WO2014109373A1 - 成形体、およびその製造方法 - Google Patents

成形体、およびその製造方法 Download PDF

Info

Publication number
WO2014109373A1
WO2014109373A1 PCT/JP2014/050255 JP2014050255W WO2014109373A1 WO 2014109373 A1 WO2014109373 A1 WO 2014109373A1 JP 2014050255 W JP2014050255 W JP 2014050255W WO 2014109373 A1 WO2014109373 A1 WO 2014109373A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin layer
resin
layer
molded body
molded
Prior art date
Application number
PCT/JP2014/050255
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
孝之 渡邊
河野　正彦
記央 佐藤
Original Assignee
三菱樹脂株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to JP2014556444A priority Critical patent/JPWO2014109373A1/ja
Publication of WO2014109373A1 publication Critical patent/WO2014109373A1/ja

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—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
    • 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
    • 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
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/006—Using vacuum
    • 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
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/08—Deep drawing or matched-mould forming, i.e. using mechanical means only
    • 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
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/007—Hardness
    • 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

Definitions

  • the present invention relates to a surface protection panel used by being arranged on the front side (viewing side) of an image display device, in particular, a front cover material such as a mobile phone or a liquid crystal pen tablet having a touch panel function, an in-vehicle display, a guide plate or a display plate. It is related with the molded object which can be used conveniently as. That is, the present invention relates to a molded body obtained by thermoforming a resin laminate for molding by vacuum molding or pressure molding.
  • glass has been widely used from the viewpoint of hardness, heat resistance, and transparency in the fields of display covers for electronic devices.
  • glass is easily broken by impact and the weight of the glass itself is heavy, an alternative to plastic is being studied.
  • acrylic resins are widely used because of their high transparency and excellent surface hardness.
  • acrylic resins are very brittle, the processing method is generally performed by cutting, and it cannot be said that the productivity is high.
  • Patent Document 1 In order to eliminate brittleness and low scratch resistance, which are disadvantages of acrylic resins, for example, in Patent Document 1, a total thickness of 50 to 120 ⁇ m thick acrylic resin laminated on one side of a polycarbonate resin sheet by coextrusion. A structure in which a hard coat layer is further added to a laminate having a thickness of 0.5 to 1.2 mm has been proposed.
  • the thickness of the layer containing the acrylic resin which comprises the laminated body containing polycarbonate resin, and the total thickness of this laminated body are controlled to a specific range, and also on the layer containing an acrylic resin, or the layer containing an acrylic resin
  • a laminate including a polycarbonate resin suitable for a liquid crystal display cover having a balanced surface hardness, particularly pencil hardness, and impact resistance has been proposed by performing a hard coat treatment on a substrate including a polycarbonate resin.
  • Patent Document 3 proposes a decorative film provided with a hard coat layer by a post-curing method in which a film provided with an ultraviolet curable hard coat layer is cured by UV irradiation after decorative molding.
  • Patent Documents 4 and 5 propose a resin molded body having a hard coat layer as an improvement of the above-described thermoformability and secondary processability.
  • Patent Documents 6 and 7 propose a technique for obtaining a molded product by insert molding or in-mold molding in a laminate having a curable resin layer.
  • an object of the present invention is a molded body obtained by thermoforming a resin laminate for molding having excellent surface hardness and thermoformability, and has a beautiful appearance without whitening, cracking, foaming, and the like. Another object of the present invention is to provide a molded article having a high surface hardness.
  • the molded body according to the present invention includes a resin layer C formed from the thermoplastic resin composition c, a resin layer A formed from the thermoplastic resin composition a, and a resin layer B formed from the curable resin composition b.
  • the pencil hardness of the surface of the resin layer B is 5H or more, and the drawing depth of the molded body is 1 mm or more and 40 mm or less.
  • the molded body proposed by the present invention is obtained by thermoforming a molding resin laminate having excellent surface hardness and thermoformability, and is disposed on the front side (viewing side) of the image display device. It can be suitably used as a front cover material for a surface protection panel to be used, particularly a mobile phone having a touch panel function, a liquid crystal pen tablet, an in-vehicle display, a guide plate or a display plate. That is, the molded article proposed by the present invention is formed from the resin layer C formed from the thermoplastic resin composition c, the resin layer A formed from the thermoplastic resin composition a, and the curable resin composition b.
  • thermoforming a resin laminate for molding formed by laminating at least three layers of the resin layer B in this order and has a beautiful appearance with no whitening, cracks, foaming, etc., and excellent surface hardness It is. Furthermore, it can cope with complicated shapes having various drawing depths.
  • the structure of one Embodiment is illustrated about the resin laminated body for shaping
  • the structure of one Embodiment is illustrated.
  • main molded body a molded body (referred to as “main molded body”) as an example of an embodiment of the present invention will be described.
  • present invention is not limited to the present molded body.
  • the molded body according to the first invention includes a resin layer C formed from the thermoplastic resin composition c, a resin layer A formed from the thermoplastic resin composition a, and a resin formed from the curable resin composition b. It is obtained by thermoforming a molding resin laminate obtained by laminating at least three layers of layer B in this order, and is a molded product having the following characteristics.
  • the pencil hardness of the surface of the resin layer B is 5H or more, and the drawing depth of the molded body is 1 mm or more and 40 mm or less.
  • the in-mold molded product according to the present invention is formed by injection molding a molten resin on the resin layer C side of the molded product to form a backing layer.
  • the lower limit of the drawing depth of the molded body according to the present invention is preferably 1 mm or more, and more preferably 3 mm or more. If the squeezing depth is 1 mm or more, the curable resin composition b for forming the resin layer B can be selected from a wide range, for example, an organic or organic / inorganic hybrid hard coat agent. It is preferable because excellent surface hardness can be imparted to the molding resin laminate. On the other hand, the upper limit value is preferably 40 mm or less, and more preferably 20 mm or less. If the drawing depth is 40 mm or less, it is preferable because the thinning due to the expansion and deformation of the resin layer B is suppressed and excellent surface hardness is maintained in the resin laminate for molding, that is, the main molded body.
  • the molded body can be obtained by thermoforming the molding resin laminate without causing whitening or cracking while maintaining its excellent surface hardness.
  • the resin layer A and the resin layer B having a storage elastic modulus in which the molding resin laminate satisfies the following relationship at a predetermined temperature (I):
  • the resin layer C ⁇ 2.0 (GPa) ⁇ Storage modulus of resin layer B ⁇ Storage modulus of resin layer A ⁇ 2.5 (GPa) ⁇ 1.0 (GPa) ⁇ Storage modulus of resin layer A ⁇ Storage modulus of resin layer C ⁇ 1.0 (GPa)
  • the predetermined temperature (I) refers to the glass transition temperature of the resin layer A ⁇ 20 ° C.
  • the lower limit of the difference in storage elastic modulus between the resin layer B and the resin layer A at a predetermined temperature (I) is preferably ⁇ 2.0 (GPa) or more, more preferably ⁇ 1.5 (GPa) or more. Particularly preferably, it is ⁇ 1.0 (GPa) or more.
  • a difference in storage elastic modulus of ⁇ 2.0 (GPa) or more is preferable because excellent surface hardness is maintained in the molded body.
  • the upper limit value of the difference in storage elastic modulus is preferably 2.5 (GPa) or less. When the storage elastic modulus difference is 2.5 (GPa) or less, the resin layer B is easily shaped following the deformation of the resin layer A when the molding resin laminate is thermoformed. For this reason, the difference in storage elastic modulus is more preferably 2.0 (GPa) or less, and particularly preferably 1.5 (GPa) or less.
  • the lower limit of the difference in storage modulus between the resin layer A and the resin layer C at a predetermined temperature (I) is preferably ⁇ 1.0 (GPa) or more, more preferably ⁇ 0.5 (GPa) or more. Yes, particularly preferably ⁇ 0.1 (GPa) or more. If the lower limit of the difference in storage modulus is ⁇ 1.0 (GPa) or more, it is preferable because excellent surface hardness is maintained in the molded body. On the other hand, the upper limit of the difference in storage elastic modulus is 1.0 (GPa) or less, more preferably 0.7 (GPa) or less, and particularly preferably 0.5 (GPa) or less.
  • the resin layer C is easily shaped following the deformation of the resin layer A when the resin laminate for molding is thermoformed. It is preferable because the moldability is good. Furthermore, it is preferable because the rigidity of the molded body is maintained and the handling property is improved.
  • the molding resin laminate has an elongation rate of 6% or more and 50% or less at a predetermined temperature (II). It is mentioned that it has.
  • the predetermined temperature (II) refers to the glass transition temperature of the resin layer A ⁇ 30 ° C.
  • the lower limit value of the elongation rate of the molding resin laminate is preferably 6% or more.
  • the elongation rate is 6% or more, when the molding resin laminate is thermoformed, cracks and cracks do not occur on the surface of the molded body, and good thermoformability can be obtained.
  • drawing can be performed by a press molding method.
  • the elongation ratio is 15% or more because, for example, drawing can be performed by a press molding method or a vacuum / pressure forming method, and thermoforming can be performed in a wide temperature range.
  • the upper limit of the elongation rate of the molding resin laminate is preferably 50% or less, and more preferably 30% or less. An elongation of 50% or less is preferable because sufficient surface hardness can be maintained for the molded body.
  • the pencil hardness of the surface of the resin layer B constituting the molded body is preferably 5H or more, and more preferably 7H or more. If the pencil hardness on the surface of the resin layer B is 5H or more, a molded article having excellent surface hardness can be provided.
  • the number of reciprocations until a scratch is generated is preferably 50 times or more.
  • the number of reciprocations until the surface is scratched when rubbed with the steel wool is 50 times or more, it is possible to provide a molded article having excellent scratch resistance and being hardly scratched. From this point of view, the number of reciprocations until the surface is scratched is preferably 50 times or more, more preferably 100 times or more, and particularly preferably 500 times or more.
  • the molded body includes at least three of a resin layer C formed from the thermoplastic resin composition c, a resin layer A formed from the thermoplastic resin composition a, and a resin layer B formed from the curable resin composition b.
  • a molding resin laminate formed by laminating layers in this order is formed by thermoforming.
  • the resin layer A is arranged on the back side of the resin layer B, thereby playing a role of making the resin layer B exhibit excellent surface hardness.
  • the resin layer A behaves like a hard underlayer, for example, when measuring pencil hardness, a high-hardness needle shape such as a pencil lead.
  • the resin layer A itself acts to repel and prevent the object from biting into the resin layer B, the resin layer B is prevented from being scratched or scraped by a needle-like object such as a pencil lead, ie, excellent in the resin layer B. It is preferable because the surface hardness can be expressed.
  • a high-hardness needle-like object such as a pencil lead bites into the resin layer B, and the resin layer A itself absorbs in a depressed manner. It cannot be obstructed, and a high-hardness needle-like object such as a pencil lead bites in and the resin layer B is easily scratched or scraped.
  • the hardness of the surface of the resin layer A is preferably a pencil hardness of 3H or more, and more preferably 5H or more. If the pencil hardness on the surface of the resin layer A is 3H or more, it is preferable because excellent hardness is maintained on the surface of the resin layer B even if the thickness of the resin layer B laminated thereon is reduced.
  • the resin layer A having a surface pencil hardness of 3H or more is disposed on the back side of the resin layer B, the resin layer A behaves like a hard underlayer as described above, for example, when measuring pencil hardness, a pencil lead, etc.
  • the resin layer A itself acts to repel and prevent the high hardness needle-like object from biting into the resin layer B, the needle-like object such as a pencil lead bites into the resin layer B even if the resin layer B is thin. It is preferable because scratches and scrapes are prevented from occurring, that is, excellent hardness is maintained on the surface of the resin layer B.
  • the pencil hardness of the surface of the resin layer A disposed on the back side of the resin layer B is 2H or less, the resin layer A itself can be prevented from biting into the resin layer B by a high hardness needle-like object such as a pencil lead.
  • the resin layer B Since the surface hardness is insufficient, it is necessary to prevent the resin layer B from being scratched or scraped by increasing the thickness of the resin layer B and making it difficult to dent, thereby causing a high-hardness needle-like object such as a pencil lead to bite in. There is. If the thickness of the resin layer B can be reduced, it is preferable that the resin layer B is easily formed following the deformation of the resin layer A when the molding resin laminate is thermoformed.
  • thermoplastic resin composition a The resin layer A in the molded body is formed from the thermoplastic resin composition a.
  • the thermoplastic resin that can be used for the thermoplastic resin composition a is not particularly limited as long as it is a thermoplastic resin that can form a film, a sheet, or a plate by melt extrusion.
  • Preferred examples include polyethylene terephthalate, Polyester resins typified by aromatic polyesters such as polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, and aliphatic polyesters such as polylactic acid polymers, polyethylene, polypropylene , Polyolefin resins such as cycloolefin resins, polycarbonate resins, acrylic resins, polystyrene resins, polyamide resins, polyether resins, polyurethane resins, polyphenylenes Rufide resin, polyester amide resin, polyether ester resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polyphenylene ether resin, polyarylate resin, polysulfone resin , Polyetherimide resins, polyamideimide resins, polyimide resins
  • polyester resins, polycarbonate resins, and acrylic resins are preferable from the viewpoint that there is almost no absorption in the visible light region.
  • the pencil hardness of the surface of the resin layer A is preferably 3H or more in terms of expressing the excellent surface hardness of the resin layer B as described above, and the thermoplastic resin composition for forming the resin layer A from this point.
  • the main component of the product a is particularly preferably an acrylic resin.
  • the thermoplastic resin composition a which comprises the resin layer A is a mixture of 2 or more types of resin chosen from the above-mentioned, and they are incompatible with each other, the volume fraction is the highest.
  • the glass transition temperature of the thermoplastic resin is defined as the glass transition temperature of the resin layer A.
  • acrylic resin examples include methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopenteny
  • the monomer copolymerizable with the monomer constituting the acrylic resin may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule.
  • the polyfunctional monomer may be a compound having at least two polymerizable carbon-carbon double bonds in the molecule.
  • monofunctional monomers include aromatic alkenyl compounds such as styrene, ⁇ -methylstyrene, and vinyl toluene; alkenyl cyan compounds such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimides; and the like.
  • polyfunctional monomers examples include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate; allyl acrylate, allyl methacrylate, cinnamon Alkenyl esters of unsaturated carboxylic acids such as allyl acid; polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate; aromatic polyalkenyl compounds such as divinylbenzene; etc. Is mentioned. Two or more types of monomers that can be copolymerized with alkyl methacrylate or alkyl acrylate may be used as necessary.
  • a methyl methacrylate-styrene copolymer is preferably used from the viewpoint of improving the environmental resistance (warpage due to moisture absorption) of the acrylic resin. I can do it.
  • the methyl methacrylate-styrene copolymer resin those having a methyl methacrylate unit of 30 to 95% by weight and a styrene unit of 5 to 70% by weight are generally used based on the total monomer units, preferably methyl methacrylate.
  • Those having a unit of 40 to 95% by weight and styrene units of 5 to 60% by weight are used, more preferably those having 50 to 90% by weight of methyl methacrylate units and 10 to 50% by weight of styrene units.
  • the breaking strength of the surface layer itself is lowered, the whole film is easily broken, and the surface hardness is also lowered.
  • the ratio of a methylmethacrylate unit becomes large, environmental resistance will fall.
  • the acrylic resin that can be used in the present invention can be prepared by polymerizing the above-described monomer components by a known method such as suspension polymerization, emulsion polymerization, or bulk polymerization. At that time, it is preferable to use a chain transfer agent during the polymerization in order to adjust the glass transition temperature to a desired value or to obtain a viscosity showing a suitable moldability when producing a molding resin laminate.
  • the amount of the chain transfer agent may be appropriately determined according to the type of monomer component and the composition thereof.
  • the acrylic resin which has heat resistance can also be preferably used as the thermoplastic resin composition a.
  • the resin layer A is formed using a heat-resistant acrylic resin as a main component of the thermoplastic resin composition a, it is preferable in this molded body because it may be easy to impart not only heat resistance but also excellent thermoformability. .
  • the molding resin laminate is formed by laminating at least three layers of the resin layer C, the resin layer A, and the resin layer B in this order, of which the glass transition temperature of the resin layer A and the resin layer C is If the absolute value of the difference is within 30 ° C., the conditions for obtaining the molded body, that is, the conditions for thermoforming the molded resin laminate without causing whitening or cracking while maintaining its excellent surface hardness. Since it is easy to obtain, it is preferable. In the case where the main component of the thermoplastic resin composition c forming the resin layer C has a high glass transition temperature, it is preferable that the acrylic resin has a high glass transition temperature as well, from this point of view. A heat-resistant acrylic resin can be advantageously used.
  • the heat resistant acrylic resin a1 is a copolymer resin containing a (meth) acrylic acid ester structural unit represented by the following general formula (1) and an aliphatic vinyl structural unit represented by the following general formula (2). The thing characterized by this is mentioned.
  • R1 is hydrogen or a methyl group
  • R2 is an alkyl group having 1 to 16 carbon atoms.
  • R3 is hydrogen or a methyl group
  • R4 is a cyclohexyl group having an alkyl substituent having 1 to 4 carbon atoms.
  • R2 of the (meth) acrylic ester structural unit represented by the general formula (1) is an alkyl group having 1 to 16 carbon atoms, and is a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, or isobornyl. Examples include groups. These can be used alone or in combination of two or more. Of these, a (meth) acrylic acid ester structural unit in which R2 is a methyl group and / or an ethyl group is preferable, and a methacrylic acid ester structural unit in which R1 is a methyl group and R2 is a methyl group is more preferable.
  • Examples of the aliphatic vinyl structural unit represented by the general formula (2) include those in which R3 is hydrogen or a methyl group, R4 is a cyclohexyl group or a cyclohexyl group having an alkyl group having 1 to 4 carbon atoms. Can do. These can be used alone or in combination of two or more. Of these, preferred are aliphatic vinyl structural units in which R3 is hydrogen and R4 is a cyclohexyl group.
  • the molar composition ratio between the (meth) acrylic acid ester structural unit represented by the general formula (1) and the aliphatic vinyl structural unit represented by the general formula (2) is in the range of 15:85 to 85:15. Yes, preferably in the range of 25:75 to 75:25, and more preferably in the range of 30:70 to 70:30. If the molar composition ratio of the (meth) acrylic ester structural unit to the total of the (meth) acrylic ester structural unit and the aliphatic vinyl structural unit is less than 15%, the mechanical strength becomes too low and becomes brittle. Absent. If it exceeds 85%, the heat resistance may be insufficient.
  • the heat-resistant acrylic resin a1 is mainly composed of a (meth) acrylic acid ester structural unit represented by the general formula (1) and an aliphatic vinyl structural unit represented by the general formula (2).
  • (meth) acrylic acid shows methacrylic acid and / or acrylic acid.
  • aromatic vinyl monomer used at this time include styrene, ⁇ -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.
  • (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
  • (Meth) acrylic acid cyclohexyl (meth) acrylic acid alkyl (meth) acrylates such as isobornyl, etc., but from the balance of physical properties, alkyl methacrylate is used alone, or alkyl methacrylate and It is preferable to use alkyl acrylate together.
  • alkyl methacrylates methyl methacrylate and ethyl methacrylate are particularly preferable.
  • the aromatic vinyl monomer It is preferable that 70% or more of the aromatic ring is obtained by hydrogenation. That is, the proportion of the aromatic vinyl structural unit in the heat resistant acrylic resin a1 is preferably 30% or less in the heat resistant acrylic resin a1. If it is in the range exceeding 30%, the transparency of the heat-resistant acrylic resin a1 may be lowered. More preferably, it is the range of 20% or less, More preferably, it is the range of 10% or less.
  • a known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer.
  • a known method can be used.
  • it can be produced by a bulk polymerization method or a solution polymerization method.
  • a solution polymerization method a monomer composition containing a monomer, a chain transfer agent, and a polymerization initiator is continuously supplied to a complete mixing tank and is continuously polymerized at 100 to 180 ° C.
  • the method for hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out batchwise or continuously with a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. When the temperature is 60 ° C. or higher, the reaction time does not take too long, and when it is 250 ° C. or lower, the molecular chain is not broken and the ester moiety is not hydrogenated.
  • Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium and rhodium or oxides or salts or complex compounds of these metals, carbon, alumina, silica, silica / alumina, diatomaceous earth. And a solid catalyst supported on a porous carrier.
  • the glass transition temperature of the heat-resistant acrylic resin a1 is preferably 110 ° C. or higher. If the glass transition temperature is 110 ° C. or higher, the heat resistance of the laminate will not be insufficient.
  • the heat-resistant acrylic resin a2 is based on all monomer units constituting the acrylic resin, based on 60 to 95% by weight of methyl methacrylate units, methacrylic acid units, acrylic acid units, maleic anhydride units, N- Examples thereof include a polymer having 5 to 40% by weight of a unit selected from a substituted or unsubstituted maleimide unit, a glutaric anhydride structural unit, and a glutarimide structural unit and having a glass transition temperature of 110 ° C. or higher.
  • the methyl methacrylate unit is a unit [—CH 2 —C (CH 3 ) (CO 2 CH 3 ) —] formed by polymerization of methyl methacrylate, and the methacrylic acid unit is obtained by polymerization of methacrylic acid.
  • the maleic anhydride unit is a unit formed by polymerization of maleic anhydride represented by the general formula (3), and the N-substituted or unsubstituted maleimide unit is represented by the general formula (4). Units formed by polymerization of N-substituted or unsubstituted maleimides.
  • R 1 represents a hydrogen atom or a substituent.
  • substituents include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, and a phenyl group.
  • An aryl group such as an aryl group or a benzyl group, and the carbon number thereof is usually about 1 to 20.
  • the glutaric anhydride structural unit is a unit having a glutaric anhydride structure
  • the glutarimide structural unit is a unit having a glutarimide structure.
  • each of the following general formula (5) and It is shown by (6).
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 represents a hydrogen atom or a substituent
  • examples of the substituent include a methyl group
  • an alkyl group such as an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group
  • the number of carbon atoms is usually about 1 to 20.
  • Methyl methacrylate units, methacrylic acid units, acrylic acid units, maleic anhydride units, and N-substituted or unsubstituted maleimide units are used as polymerization raw materials for methyl methacrylate, methacrylic acid, acrylic acid, maleic anhydride, respectively. , And N-substituted or unsubstituted maleimides.
  • the glutaric anhydride structural unit may be a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid and / or acrylic acid, such as sodium hydroxide, potassium hydroxide, sodium methylate. It can be introduced by modification by heat treatment in the presence of a basic compound, usually at 150 to 350 ° C., preferably 220 to 320 ° C.
  • the glutarimide structural unit is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid and / or acrylic acid, usually in the presence of ammonia or a primary amine at 150 to 350 ° C., Preferably, it can be introduced by modifying by heat treatment in the range of 220 to 320 ° C.
  • the monomer unit composition of the acrylic resin is preferably 65 to 95% by weight, more preferably 70 to 92% by weight of methyl methacrylate units.
  • the unit selected from maleic anhydride units, N-substituted or unsubstituted maleimide units, glutaric anhydride structural units, and glutarimide structural units is preferably 5 to 35% by weight, more preferably 8 to 30% by weight. It is.
  • the glass transition temperature of the acrylic polymer is preferably 115 ° C. or higher, and usually 150 ° C. or lower.
  • heat resistant acrylic resin a3 examples include those having a lactone ring structure formed by cyclization condensation reaction of a polymer ( ⁇ ) having a hydroxyl group and an ester group in the molecular chain.
  • the polymer ( ⁇ ) is a copolymer obtained by polymerizing a monomer component containing at least a (meth) acrylate monomer ( ⁇ 1) and a 2- (hydroxyalkyl) acrylate monomer, and the lactone
  • the ring structure is a structure represented by the following general formula (7).
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
  • the organic residue may contain an oxygen atom.
  • the polymer ( ⁇ ) having a hydroxyl group and an ester group in the molecular chain for example, a (meth) acrylate monomer ( ⁇ 1)
  • a polymer obtained by polymerizing a monomer component containing a vinyl monomer ( ⁇ 2) having a structural unit represented by the following general formula (8) is preferred.
  • R 4 and R 5 each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
  • the (meth) acrylate monomer ( ⁇ 1) is a so-called (meth) other than the vinyl monomer having the 2- (hydroxymethyl) acrylate structural unit represented by the general formula (8). If it is an acrylic acid alkylester monomer, it will not specifically limit. For example, an aliphatic (meth) acrylate having an alkyl group or the like, an alicyclic (meth) acrylate having a cyclohexyl group or the like, or an aromatic (meth) acrylate having a benzyl group or the like may be used. In addition, a desired substituent or functional group may be introduced into these groups.
  • the (meth) acrylate monomer ( ⁇ 1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Acrylic acid ester and the like. These may be used alone or in combination of two or more.
  • methyl methacrylate and methyl acrylate are preferable, and in terms of the surface hardness of the resulting acrylic resin, methyl methacrylate is more preferable.
  • (meth) acrylate having a cyclohexyl group is preferable in that it imparts hydrophobicity to the acrylic resin and, as a result, can reduce the water absorption rate of the acrylic resin and can impart weather resistance to the acrylic resin.
  • (meth) acrylate having an aromatic group is preferable in that the aromatic ring can further improve the heat resistance of the resulting acrylic resin.
  • the proportion of the (meth) acrylate monomer ( ⁇ 1) in the monomer component is not particularly limited, but is preferably 95 to 10% by weight, more preferably 90 to 10% by weight. Further, in order to maintain good transparency and weather resistance, it is preferably 90 to 40% by weight, more preferably 90 to 60% by weight, and still more preferably 90 to 70% by weight in the total monomer components. % Should be good.
  • an unsaturated monocarboxylic acid ( ⁇ 1 ′) may be used in combination as the (meth) acrylate monomer ( ⁇ 1).
  • an unsaturated monocarboxylic acid ( ⁇ 1 ′) in combination, an acrylic resin into which a glutaric anhydride ring structure is introduced together with a lactone ring structure can be obtained, and heat resistance and mechanical strength can be further improved. It is preferable because it is possible.
  • the unsaturated monocarboxylic acid ( ⁇ 1 ′) include (meth) acrylic acid, crotonic acid, and ⁇ -substituted acrylic acid monomers which are derivatives thereof, but are not particularly limited.
  • (Meth) acrylic acid is preferred, and methacrylic acid is preferred from the viewpoint of heat resistance.
  • the ester group derived from the (meth) acrylate monomer ( ⁇ 1) in the polymer ( ⁇ ) may have a structure equivalent to that of the unsaturated carboxylic acid ( ⁇ 1 ′) depending on conditions such as heating.
  • the carboxyl group possessed by the unsaturated carboxylic acid ( ⁇ 1 ′) may have a structure of a salt such as a metal salt such as a sodium salt, as long as it does not interfere with the cyclization condensation reaction described later.
  • the ratio of the unsaturated monocarboxylic acid ( ⁇ 1 ′) is not particularly limited, and may be appropriately set within a range not impairing the effects of the present invention.
  • Examples of the vinyl monomer ( ⁇ 2) having the structural unit represented by the general formula (8) include 2- (hydroxyalkyl) acrylic acid derivatives. Specifically, 2- (hydroxymethyl) acrylic acid ester monomers are preferred. More specifically, for example, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, normal butyl 2- (hydroxymethyl), -(Hydroxymethyl) acrylic acid-t-butyl butyl and the like can be mentioned, among which methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are preferred. Further, methyl 2- (hydroxymethyl) acrylate is most preferred because it has a high effect of improving surface hardness, hot water resistance or solvent resistance. In addition, these may use only 1 type or may use 2 or more types together.
  • the ratio of the vinyl monomer ( ⁇ 2) having the structural unit represented by the general formula (8) in the monomer component is not particularly limited, but is preferably 5 to 50% by weight. . More preferably, it is 10 to 40% by weight, and more preferably 15 to 35% by weight.
  • the proportion of the vinyl monomer ( ⁇ 2) is less than the above range, the amount of the ring structure is reduced, so that the surface hardness of the laminate may be lowered, and the hot water resistance and solvent resistance may be lowered. Moreover, the heat resistance of the laminate may be lowered.
  • the amount is more than the above range, when a lactone ring structure is formed, a crosslinking reaction occurs and gelation tends to occur, the fluidity is lowered, and melt molding may be difficult.
  • a polymerizable monomer other than the above ( ⁇ 1) and ( ⁇ 2) can be used as long as the effects of the present invention are not impaired.
  • examples thereof include styrene, vinyl toluene, ⁇ -methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate and the like. In addition, these may use only 1 type or may use 2 or more types together.
  • the polymerizable monomer is used in combination as a monomer component for obtaining the polymer ( ⁇ )
  • the content of these monomers is 0 to 30% by weight or less in the monomer component.
  • it is 0 to 20% by weight or less, more preferably 0 to 10% by weight or less.
  • physical properties such as weather resistance, surface gloss or transparency, which are good physical properties derived from a (meth) acrylate monomer, may be impaired.
  • the heat resistant acrylic resin a3 is obtained by forming a ring structure by subjecting the polymer ( ⁇ ) to a cyclization condensation reaction.
  • the cyclocondensation reaction is a reaction in which a hydroxyl group and an ester group (or more carboxyl group) present in the molecular chain of the polymer ( ⁇ ) are cyclized and condensed to form a lactone ring structure by heating, Alcohol and water are by-produced by cyclization condensation.
  • a hydroxyl group and an ester group (or more carboxyl group) present in the molecular chain of the polymer ( ⁇ ) are cyclized and condensed to form a lactone ring structure by heating, Alcohol and water are by-produced by cyclization condensation.
  • Examples of a method for obtaining an acrylic resin having a lactone ring structure by cyclization condensation of the polymer ( ⁇ ) include 1) cyclization condensation by heating the polymer ( ⁇ ) under reduced pressure in an extruder. Method of reaction (Polym. Prepr., 8, 1,576 (1967), 2) The cyclization condensation reaction of the polymer ( ⁇ ) is carried out in the presence of a solvent, and depolymerization is performed simultaneously with the cyclization condensation reaction. There are a method of volatilization, 3) a method of cyclocondensing the polymer ( ⁇ ) using a specific organophosphorus compound as a catalyst (European Patent No. 1008606), and the like.
  • the present invention is not limited to these, and a plurality of methods among the methods 1) to 3) may be adopted.
  • the reaction rate of the cyclization condensation reaction is high, it is possible to suppress the foam and silver streak from entering the laminate, and the reduction in mechanical strength due to the decrease in molecular weight during devolatilization can be suppressed 2) And 3) are preferred.
  • the heat-resistant acrylic resin a3 used in the present invention has a weight average molecular weight of 1,000 to 1,000,000, more preferably 5,000 to 500,000, and most preferably 50,000 to 300,000. Is preferred.
  • weight average molecular weight is lower than the above range, not only the surface hardness, hot water resistance or solvent resistance is lowered, but also there is a problem that the mechanical strength is lowered and it is likely to become brittle. This is not preferable because the properties are lowered and the molding becomes difficult.
  • the glass transition temperature (Tg) of the heat-resistant acrylic resin a3 is preferably 115 ° C. or higher, more preferably 125 ° C. or higher, and most preferably 130 ° C. or higher.
  • the resin layer A As described above, it is preferable to form the resin layer A with the thermoplastic resin composition a mainly containing any one of the above heat-resistant acrylic resins because suitable conditions for obtaining the molded article are satisfied.
  • the molding resin laminate is formed by laminating at least three layers of a resin layer C, a resin layer A, and a resin layer B in this order.
  • the molding resin laminate is a main component of the thermoplastic resin composition c that forms the resin layer C. If a polycarbonate-based resin is used, the glass transition temperature between the resin layer A and the resin layer C can be used even if any of the above heat-resistant acrylic resins is used as the main component of the thermoplastic resin composition a forming the resin layer A.
  • the absolute value of the difference can be within 30 ° C.
  • thermoforming of the molding resin laminate can be performed without causing whitening, cracking, and further foaming. This is preferable because it becomes possible.
  • Heat resistant acrylic resin a4 As the heat-resistant acrylic resin a4, not only heat resistance but also an excellent hardness can be used in which a hard dispersed phase is contained in an acrylic resin matrix. More specifically, an acrylic resin containing and dispersing a hard dispersed phase material that has better heat resistance or scratch resistance than the acrylic resin can be used. By using an acrylic resin containing a hard dispersed phase in the matrix, the pencil hardness of the surface of the resin layer A can be 5H or more.
  • thermosetting resins examples include thermosetting resins. Specifically, phenol resins, amino resins, epoxy resins, silicone resins, thermosetting polyimide resins, thermosetting polyurethane resins, etc.
  • addition polymerization resins obtained by radical polymerization of unsaturated monomers such as thermosetting acrylic resins, vinyl ester resins, unsaturated polyester resins, diallyl phthalate resins, etc. It is done.
  • the unsaturated monomer is a polyfunctional one, it is preferable because the characteristics (insoluble, high glass transition temperature) of a hard material can be obtained by polymerization crosslinking.
  • unsaturated monomers include polyols and polyesters of acrylic acid and / or methacrylic acid, as well as crosslinkable monomers such as polyaryls and polyvinyl ethers of these polyols. However, it is not limited to these.
  • the unsaturated monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethoxylate (di-, tri-) acrylate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, penta Examples include erythritol tetraallyl ether, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, or ethoxylated pentaerythritol tetraacrylate, and mixtures thereof.
  • TMPTA trimethylolpropane triacrylate
  • TMPTMA trimethylolpropane trimethacrylate
  • Thermosetting resins may be used alone or in combination of two or more. Moreover, you may use combining these thermosetting resins and the thermoplastic resin which has the unsaturated bond which can be bridge
  • Examples of the shape of the hard dispersed phase include particles, spheres, lines, fibers, and the like. From the viewpoint of being easily dispersed evenly in the acrylic resin that is a thermoplastic matrix resin, a sphere is preferable. However, it is not limited to this.
  • the particle size of the hard dispersed phase is appropriately set according to the purpose and application of the molded body, but is preferably 0.1 to 1000 ⁇ m.
  • the blending amount of the hard dispersed phase in the acrylic resin phase is appropriately set according to the purpose and application of the molded body, but is preferably 0.1 to 60% by weight.
  • thermosetting resin material constituting a hard dispersed phase is added to the acrylic resin material.
  • a hard dispersed phase can be formed by causing phase separation and crosslinking.
  • the thermosetting resin may be previously molded into a particulate form, added to the acrylic resin, and kneaded and molded at a temperature at which the thermosetting resin does not dissolve.
  • thermoplastic resin composition a that forms the resin layer A includes, for example, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a flame retardant such as a silicone compound, a filler, Various additives such as glass fiber and impact modifier may be contained within a range not impairing the effects of the present invention.
  • thermoplastic resin composition a forming the resin layer A can also contain acrylic rubber particles having an elastic polymer portion as long as the effects of the present invention are not impaired.
  • acrylic rubber particles have a layer (elastic polymer layer) made of an elastic polymer mainly composed of an acrylate ester, and may be single-layer particles made only of an elastic polymer or elastic.
  • Particles having a multilayer structure composed of a polymer layer and a layer made of a hard polymer (hard polymer layer) may be used, but the surface hardness of the resin layer A disposed on the surface of the molding resin laminate may be Considering it, it is preferable that the particle has a multilayer structure. In addition, only 1 type may be sufficient as acrylic rubber particle, and 2 or more types may be sufficient as it.
  • the resin layer A is arranged on the back side of the resin layer B, thereby playing a role of causing the resin layer B to exhibit excellent surface hardness.
  • the thickness of the resin layer A is preferably 40 ⁇ m or more, and more preferably 60 ⁇ m or more. If the thickness of the resin layer A is 40 ⁇ m or more, even if the thickness of the resin layer B is reduced, an excellent surface hardness is expressed on the surface of the resin layer B, which is preferable.
  • the thickness of the resin layer A is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less. A thickness of the resin layer A of 500 ⁇ m or less is preferable because the resin layer C can easily compensate for the brittleness of the resin layer A that hinders thermoforming or punching.
  • the resin layer B in the present invention is a layer that imparts excellent surface hardness to the molded body, and at a predetermined temperature (II), the elongation ratio of the molding resin laminate including the resin layer B is set to a predetermined level. By making it within the range, excellent thermoformability can be imparted to the molding resin laminate.
  • the resin layer B is a layer having excellent scratch resistance, and when it is rubbed with a load of 500 gf using # 0000 steel wool, it is preferable that the number of reciprocations until the scratch occurs is 50 times or more. , More preferably 100 times or more, and particularly preferably 500 times or more.
  • the resin layer B of the molded body is formed from the curable resin composition b, and the curable resin composition b that can be used in the present invention is, for example, an energy beam such as an electron beam, radiation, or ultraviolet rays.
  • an energy beam such as an electron beam, radiation, or ultraviolet rays.
  • it will not specifically limit if it hardens
  • Preferred examples of the curable resin constituting the curable resin composition b include acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, carboxyl group-modified epoxy acrylate compounds, polyester acrylate compounds, copolymer acrylates, and alicyclic epoxies. Examples thereof include resins, glycidyl ether epoxy resins, vinyl ether compounds, oxetane compounds and the like. These curable resins may be used alone or in combination with a plurality of compounds.
  • examples of the curable resin imparting excellent surface hardness include radical polymerization curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, polyfunctional epoxy acrylate compounds, alkoxysilanes, and alkylalkoxys.
  • examples thereof include curable compounds of thermal polymerization type such as silane.
  • the curable resin composition b of the present invention can be an organic / inorganic composite curable resin composition obtained by adding an inorganic component to the curable resin.
  • Examples of the curable resin composition b that imparts a particularly excellent surface hardness to the molded body include an organic / inorganic hybrid curable resin composition.
  • Examples of the organic / inorganic hybrid curable resin composition include those composed of a curable resin composition containing an inorganic component having a reactive functional group in the curable resin. Utilizing an inorganic component having such a reactive functional group, for example, this inorganic component is copolymerized and crosslinked with a radical polymerizable monomer, and thus an organic / inorganic organic component is simply made to contain an inorganic component in an organic binder. Compared to the composite curable resin composition, curing shrinkage is unlikely to occur and high surface hardness can be expressed, which is preferable. Furthermore, from the viewpoint of reducing curing shrinkage, an organic / inorganic hybrid curable resin composition containing ultraviolet-reactive colloidal silica as an inorganic component having a reactive functional group can be mentioned as a more preferable example.
  • a forming method of the resin layer B for example, there is a method of forming and laminating on the surface of the resin layer A by coating the surface of the resin layer A as a paint of the curable resin composition b and then forming a cured film. Although there is, it is not limited to this method.
  • a lamination method with the resin layer A a known method is used. For example, laminating method using cover film, dip coating method, natural coating method, reverse coating method, comma coater method, roll coating method, spin coating method, wire bar method, extrusion method, curtain coating method, spray coating method, The gravure coat method etc. are mentioned.
  • a method of laminating the resin layer B on the resin layer A using a transfer sheet in which the resin layer B is formed on the release layer may be employed.
  • the curable resin composition b forming the resin layer B can contain a leveling agent as a surface adjustment component.
  • the leveling agent include silicone leveling agents and acrylic leveling agents.
  • those having a reactive functional group at the terminal are preferable, and those having a reactive functional group having two or more functionalities are more preferable. preferable.
  • polyether-modified polydimethylsiloxane having an acrylic group having double bonds at both ends for example, “BYK-UV 3500” and “BYK-UV 3530” manufactured by Big Chemie Japan Co., Ltd.
  • polyester-modified polydimethylsiloxane having an acrylic group having two double bonds at the end (“BYK-UV 3570” manufactured by BYK Japan).
  • polyester-modified polydimethylsiloxane having an acrylic group that has a stable haze value and contributes to improvement of scratch resistance is particularly preferable.
  • a photopolymerization initiator When the curable resin is cured with ultraviolet rays, a photopolymerization initiator is used.
  • the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethylketals, ⁇ -hydroxyalkylphenones, hydroxyketones, aminoalkylphenones, acylphosphine oxides and the like.
  • the addition amount of the photopolymerization initiator is generally in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable resin.
  • photopolymerization initiators can be used alone or in a mixture of two or more. Moreover, since these various photoinitiators are marketed, such a commercial item can be used. Examples of commercially available photopolymerization initiators include “IRGACURE 651”, “IRGACURE 184”, “IRGACURE 500”, “IRGACURE 1000”, “IRGACURE 2959”, “DAROCUR 1173”, “IRGACURE 907”, “IRGACURE 369”, “IRGACURE 1”, “IRGACURE 1”, “IRGACURE1” , “IRGACURE819", “IRGACURE784" [The above IRGACURE (Irgacure) series and DAROCUR series are sold by Ciba Specialty Chemicals, Inc.], "KAYACUREITTX”, “KAYACUREDETX-S”, “KAYACUREB-” “KAYACUREBMS”, “KAYACURE2-EA "[More KAYACURE (Kayacure)
  • the curable resin composition b that forms the resin layer B includes, for example, a lubricant such as a silicon compound, a fluorine compound, or a mixed compound thereof, an antioxidant, an ultraviolet absorber, Various additives such as antistatic agents, flame retardants such as silicone compounds, fillers, glass fibers, impact modifiers and the like can be contained within a range not impairing the effects of the present invention.
  • the thickness of the resin layer B is preferably in the range of 5 ⁇ m or more and 20 ⁇ m or less. If thickness is 5 micrometers or more, since sufficient hardness can be provided to the resin layer B surface, it is preferable. On the other hand, if the thickness is 20 ⁇ m or less, it is preferable because excellent thermoformability can be imparted to the molded body, and further, there is no possibility of warping, undulation, peeling, etc. accompanying the curing / shrinking of the resin layer B. This is also preferable.
  • the resin layer C plays a role of imparting secondary workability such as excellent impact resistance or punchability to the molded body.
  • thermoplastic resin composition c The resin layer C in the molded body is formed from the thermoplastic resin composition c.
  • the thermoplastic resin that can be used for the thermoplastic resin composition c is not particularly limited as long as it is a thermoplastic resin that can form a film, sheet, or plate by melt extrusion.
  • Preferred examples include polyethylene terephthalate, Polyester resins typified by aromatic polyesters such as polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, and aliphatic polyesters such as polylactic acid polymers, polyethylene, polypropylene , Polyolefin resins such as cycloolefin resins, polycarbonate resins, acrylic resins, polystyrene resins, polyamide resins, polyether resins, polyurethane resins, polyphenylenes Rufide resin, polyester amide resin, polyether ester resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, modified polyphenylene ether resin, polyarylate resin, polysulfone resin , Polyetherimide resins, polyamideimide resins, polyimide resins
  • a polyester resin, a polycarbonate resin, or an acrylic resin is preferable from the viewpoint that there is almost no absorption in the visible light region.
  • a polycarbonate resin is particularly preferable in consideration of the role of the resin layer C to impart secondary workability such as excellent impact resistance or punchability to the molded body.
  • the thermoplastic resin composition c constituting the resin layer C is a mixture of two or more kinds of resins selected from the above, and they are incompatible with each other, the volume fraction is the highest.
  • the glass transition temperature of the thermoplastic resin is defined as the glass transition temperature of the resin layer C.
  • the polycarbonate-based resin that can be used in the present invention is not particularly limited as long as it can form a film, sheet, or plate by melt extrusion. From the group of aromatic polycarbonate, aliphatic polycarbonate, and alicyclic polycarbonate. At least one selected can be used.
  • aromatic polycarbonate examples include i) those obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method, and ii) a solid phase transesterification method of a carbonate prepolymer. And iii) those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.
  • a product obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method is preferable in terms of productivity.
  • dihydric phenol examples include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis ⁇ (4-hydroxy-3,5-dimethyl) phenyl ⁇ methane, 1,1 -Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis ⁇ (4-hydroxy-3-methyl) phenyl ⁇ propane, 2,2-bis ⁇ (4-hydroxy-3,5-dimethyl) phenyl ⁇ propane, 2,2-bis ⁇ (4-hydroxy-3,5- Dibromo) phenyl ⁇ propane, 2,2-bis ⁇ (3-isopropyl-4-hydroxy) phenyl ⁇ propane, 2,2-bis (4-hydroxy-3-phenyl) phenyl ⁇ propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis
  • dihydric phenol examples include bisphenol A, 2,2-bis ⁇ (4-hydroxy-3-methyl) phenyl ⁇ propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 among those described above. -Bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, , 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and ⁇ , ⁇ '-bis (4-hydroxyphenyl) -m-diisopropylbenzene, alone or in combination with a dihydric phenol selected from the group consisting of Two or more types are preferably used, and in particular, bisphenol A alone or 1,1-bis (4-hydroxyphenyl) -3 , 3,5-trimethylcyclohexane, bisphenol A, 2,2-bis ⁇ (4-hydroxy-3-methyl) phenyl ⁇
  • Examples of the carbonylating agent include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, haloformates such as dihaloformates of dihydric phenols, and two or more of them can be used as necessary.
  • polycarbonate resins examples include aliphatic polycarbonate and alicyclic polycarbonate. What contains at least the structural unit derived from the dihydroxy compound which has a site
  • the dihydroxy compound is not particularly limited as long as a part of the molecular structure is represented by the general formula (9). Specifically, 9,9-bis (4- (2 -Hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9, 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-fur Nylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-d
  • a compound having a cyclic ether structure such as spiroglycol can be preferably used.
  • 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane (common name: spiroglycol)
  • 3, 9-bis (1,1-diethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane 3,9-bis (1,1-dipropyl-2-hydroxyethyl) ) -2,4,8,10-tetraoxaspiro (5.5) undecane.
  • polycarbonate-based resins may contain structural units derived from dihydroxy compounds other than the above-mentioned dihydroxy compounds (hereinafter may be referred to as “other dihydroxy compounds”), and other dihydroxy compounds include ethylene.
  • Glycol 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol
  • Aliphatic dihydroxy compounds such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 2,6-decalindi Methanol, 1,5-decal Alicyclic dihydroxy compounds such as dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-n
  • the thermoplastic resin composition c forming the resin layer C includes, for example, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a flame retardant such as a silicone compound, a filler, Various additives such as glass fiber and impact modifier may be contained within a range not impairing the effects of the present invention.
  • the resin layer C is laminated on the resin layer A and the resin layer B, thereby providing the molding resin laminate with particularly excellent impact resistance or secondary workability such as punchability.
  • the same role is achieved in the molded body obtained by thermoforming. From this point of view, it is important that the thickness of the resin layer C is set based on the ratio with the total thickness of the resin layer A and the resin layer B, and the thickness ratio is determined by the resin layer C thickness / (resin layer A (Thickness + resin layer B thickness), the thickness ratio is preferably 2 or more, more preferably 4 or more. A thickness ratio of 2 or more is preferable because it can impart secondary workability such as excellent impact resistance or punchability to the molded article.
  • the molded body can be obtained by thermoforming the molding resin laminate without causing whitening or cracking while maintaining its excellent surface hardness.
  • the resin layer A and the resin having a storage elastic modulus such that the molding resin laminate satisfies the following relationship at a predetermined temperature (I): It may be formed from the layer B and the resin layer C. ⁇ 2.0 (GPa) ⁇ Storage modulus of resin layer B ⁇ Storage modulus of resin layer A ⁇ 2.5 (GPa) ⁇ 1.0 (GPa) ⁇ Storage modulus of resin layer A ⁇ Storage modulus of resin layer C ⁇ 1.0 (GPa)
  • the predetermined temperature (I) refers to the glass transition temperature of the resin layer A ⁇ 20 ° C.
  • the lower limit of the difference in storage elastic modulus between the resin layer B and the resin layer A is preferably ⁇ 2.0 (GPa) or more, more preferably ⁇ 1.5 (GPa) or more, and particularly preferably ⁇ 1. 0 (GPa) or more. If the difference in storage elastic modulus is ⁇ 2.0 (GPa) or more, the curable resin composition b for forming the resin layer B is selected from a wide range such as an organic or organic / inorganic hybrid hard coat agent. This is preferable because it can impart excellent surface hardness to the molding resin laminate.
  • the upper limit of the difference in storage elastic modulus is preferably 2.5 (GPa) or less, more preferably 2.0 (GPa) or less, and particularly preferably 1.5 (GPa) or less. It is preferable that the difference in storage elastic modulus is 2.5 (GPa) or less because the resin layer B is easily shaped following the deformation of the resin layer A when the molding resin laminate is thermoformed.
  • the lower limit of the difference in storage elastic modulus between the resin layer A and the resin layer C is preferably ⁇ 1.0 (GPa) or more, more preferably ⁇ 0.5 (GPa) or more, and particularly preferably. -0.1 (GPa) or more. If the lower limit of the difference in storage modulus is ⁇ 1.0 (GPa) or more, it is preferable because the molded article can exhibit excellent surface hardness.
  • the upper limit of the difference in storage elastic modulus is preferably 1.0 (GPa) or less, more preferably 0.7 (GPa) or less, and particularly preferably 0.5 (GPa) or less.
  • the resin layer A follows the deformation of the resin layer C when the molded body is thermoformed. It is preferable because it can be shaped. Furthermore, it is also preferable in terms of maintaining the rigidity of the molded body and improving the handling properties.
  • the molding resin laminate is not less than 6% and not more than 50% at a predetermined temperature (II). It is mentioned that it has the elongation rate of.
  • the predetermined temperature (II) refers to the glass transition temperature of the resin layer A ⁇ 30 ° C.
  • the lower limit of the elongation percentage of the molding resin laminate at the predetermined temperature (II) is preferably 6% or more, and more preferably 15% or more. If the elongation is 6% or more, there is no cracking or cracking on the surface of the molded body when thermoformed, and for example, a drawing process by a press molding method is possible, and a molded body with a beautiful appearance can be obtained. Since it is obtained, it is preferable. Further, it is more preferable that the elongation ratio is 15% or more because, for example, drawing can be performed by a press molding method or a vacuum / pressure forming method, and thermoforming can be performed in a wide temperature range.
  • the upper limit of the elongation is in the range of 50% or less, preferably in the range of 30% or less. If the elongation is 50% or less, the curable resin composition c for forming the resin layer C can be selected from a wide range, for example, organic or organic / inorganic hybrid hard coat agents. Therefore, it is preferable because an excellent surface hardness can be imparted to the molded body.
  • suitable conditions for obtaining the molded body include, for example, the resin layer A having a storage elastic modulus such that the molding resin laminate satisfies a desired relationship at a predetermined temperature (I), It can be mentioned that the resin layer B and the resin layer C are formed and that the molding resin laminate has a desired elongation at a predetermined temperature (II). It is preferable that the resin laminate satisfies both conditions, but any condition may be satisfied.
  • the absolute value of the difference in glass transition temperature between the resin layer A formed from the thermoplastic resin composition a and the resin layer C formed from the thermoplastic resin composition c may be within 30 ° C. This can also be mentioned as one of means for adjusting the elongation rate of the molding resin laminate so as to be in a desired range at a predetermined temperature (II).
  • the absolute value of the glass transition temperature difference between the resin layer A and the resin layer C is within 30 ° C., the viscoelastic behavior of the resin layer A and the resin layer C approaches and the resin layer at a predetermined temperature (I). It is presumed that the storage elastic modulus of A and the resin layer C easily satisfies the desired relationship. Further, it is preferable because a temperature range satisfying a desired relationship is widened, that is, a temperature range capable of thermoforming is expected to be widened.
  • the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C indicates that the condition for obtaining the molded product, that is, the molding resin laminate has excellent surface hardness. This is preferable because it is easy to obtain conditions for thermoforming without causing whitening or cracks while maintaining the above. From this viewpoint, the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C is more preferably 25 ° C. or less, and further preferably 20 ° C. or less.
  • Examples of the method for setting the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C within 30 ° C. include the following methods. (1) In the thermoplastic resin composition a and / or the thermoplastic resin composition c, by blending thermoplastic resins having different glass transition temperatures, a mixture of at least two kinds of thermoplastic resins is obtained. A method of adjusting the difference in glass transition temperature between A and the resin layer C within 30 ° C.
  • the two or more types of thermoplastic resins having different glass transition temperatures the same or different types of thermoplastic resins can be used as long as the glass transition temperatures are different.
  • the thermoplastic resin blended here is compatible with the thermoplastic resin composition a or the thermoplastic resin composition c.
  • thermoplastic resin composition a and / or the thermoplastic resin composition c a difference in glass transition temperature between the resin layer A and the resin layer C is within 30 ° C. by using a copolymer with other components. How to adjust.
  • thermoplastic resin composition a and / or thermoplastic resin composition c by mixing additives such as plasticizer, the difference in glass transition temperature between resin layer A and resin layer C is within 30 ° C. How to adjust.
  • a desired relationship is satisfied at a predetermined temperature (I) by a method other than setting the absolute value of the difference in glass transition temperature between the resin layer A and the resin layer C to be within 30 ° C.
  • a means for forming the resin layer A having the storage modulus and the resin layer C at least two incompatible thermoplastic resins in the thermoplastic resin composition a and / or the thermoplastic resin composition c are used.
  • the method of adjusting the storage elastic modulus difference of the resin layer A and the resin layer C to a desired range can be mentioned. This may also be a method of adjusting the elongation rate of the molding resin laminate to a desired range.
  • Inorganic contained in the resin layer B as a means for forming the molding resin laminate from the resin layer A having a storage elastic modulus satisfying a desired relationship at a predetermined temperature (I) and the resin layer B
  • concentration of the inorganic component which has a component and / or a reactive functional group into the predetermined range is mentioned. This can also be mentioned as a method for adjusting the elongation ratio of the molding resin laminate to a desired range at a predetermined temperature (II).
  • the concentration of the inorganic component and / or the inorganic component having a reactive functional group contained in the resin layer B is preferably 0% by mass or more and 50% by mass or less, and preferably 0% by mass or more and 40% by mass or less. More preferred.
  • the concentration is 0% by mass or more and 50% by mass or less
  • the resin layer A and the resin layer B having a storage elastic modulus satisfying a desired relationship at a predetermined temperature (I) can be formed.
  • the elongation ratio of the molding resin laminate at a predetermined temperature (II) can be within a desired range.
  • the thermoplastic resin a has an acrylic resin as a main component in the example of (1),
  • the thermoplastic resin composition c is made of a mixture of a polycarbonate resin and other thermoplastic resins will be described in detail.
  • the thermoplastic resin composition c in the present invention can be a mixture comprising two or more thermoplastic resins as described above.
  • the absolute value of the difference between the glass transition temperatures of the two is within 30 ° C.
  • the other polycarbonate resin is mixed with the latter polycarbonate resin. That is, a method of lowering the glass transition temperature of a polycarbonate resin by melt blending (; mixing and heat-melting) a polycarbonate resin and another thermoplastic resin to form a polymer alloy.
  • the glass transition temperature of polycarbonate resin is around 150 ° C, which is higher by 50 ° C than the typical glass transition temperature of acrylic resin, 100 ° C, so other thermoplastic resins are mixed with polycarbonate resin. Thus, the glass transition temperature of the polycarbonate resin is lowered.
  • other thermoplastic resins include aromatic polyesters and polyester resins having a cyclic acetal skeleton.
  • thermoplastic resin examples include a resin obtained by condensation polymerization of an aromatic dicarboxylic acid component and a diol component.
  • typical examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like. Further, a part of terephthalic acid may be substituted with another dicarboxylic acid component.
  • examples of other dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, neopentylic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, p-oxybenzoic acid and the like. These may be one kind or a mixture of two or more kinds, and the amount of other dicarboxylic acids to be substituted can be appropriately selected.
  • diol component examples include ethylene glycol, diethylene glycol, triethylene glycol, and cyclohexanedimethanol.
  • a part of ethylene glycol may be substituted with another diol component.
  • Other diol components include propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, trimethylol, methoxypolyethylene
  • alkylene glycol examples include alkylene glycol. These may be one kind or a mixture of two or more kinds, and the amount of other diols to be substituted can be appropriately selected.
  • aromatic polyester examples include polyethylene terephthalate obtained by condensation polymerization of terephthalic acid and ethylene glycol, and polybutylene terephthalate obtained by condensation polymerization of terephthalic acid or dimethyl terephthalate and 1,4-butanediol.
  • a copolyester containing a dicarboxylic acid component other than terephthalic acid and / or a diol component other than ethylene glycol can also be mentioned as a preferred aromatic polyester.
  • a part of ethylene glycol in polyethylene terephthalate preferably a copolyester having a structure in which 55 to 75 mol% is substituted with cyclohexanedimethanol, or a part of terephthalic acid in polybutylene terephthalate, preferably May include a copolyester having a structure in which 10-30 mol% is substituted with isophthalic acid, or a mixture of these copolyesters.
  • aromatic polyesters described above it is preferable to select those that can be polymer-alloyed by melt blending with a polycarbonate resin and that can sufficiently lower the glass transition temperature of the polycarbonate resin.
  • These copolyesters are known to be completely compatible and polymerized by melt blending with a polycarbonate-based resin, and the glass transition temperature can be effectively lowered.
  • polyester resin d2 having a cyclic acetal skeleton (Polyester resin d2 having a cyclic acetal skeleton)
  • the polyester resin d2 having a cyclic acetal skeleton that can be used as another thermoplastic resin is a polyester resin that contains a dicarboxylic acid unit and a diol unit, and 1 to 60 mol% of the diol unit is a diol unit having a cyclic acetal skeleton. is there.
  • the diol unit having a cyclic acetal skeleton is preferably a unit derived from a compound represented by the following general formula (10) or (11).
  • R 1 , R 2 , and R 3 are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups.
  • the compounds of the general formulas (10) and (11) include 3,9-bis (1,1-dimethyl-2-hydroxyethyl)-) 2,4, 8,10-tetraoxaspiro [5.5] undecane, or 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane is particularly preferred.
  • diol units other than the diol units having a cyclic acetal skeleton are not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentane.
  • Aliphatic diols such as diol, 1,6-hexanediol, diethylene glycol, propylene glycol and neopentyl glycol; polyether diols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; 1,3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 1,2-decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5- Alicyclic such as decahydronaphthalene diethanol, 1,6-decahydronaphthalene diethanol, 2,7-decahydro naphthalene diethanol, tetralin dimethanol, norbornane dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol Diols such as 4,4 ′-(1-methylethylidene) bisphenol, methylene bisphenol (
  • Aromatic dihydroxy compounds such as E sulfonyl benzophenone; and alkylene oxide adducts of the above aromatic dihydroxy compounds can be exemplified.
  • ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol are preferred, and ethylene glycol is particularly preferred.
  • the exemplified diol units can be used alone or in combination.
  • the dicarboxylic acid unit of the polyester resin d2 having a cyclic acetal skeleton used in the present invention is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane.
  • Aliphatic dicarboxylic acids such as dicarboxylic acid, cyclohexanedicarboxylic acid, decanedicarboxylic acid, norbornanedicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclododecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, 1, Examples include aromatic dicarboxylic acids such as 4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetralindicarboxylic acid.
  • terephthalic acid isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid and 2,7-naphthalene
  • Aromatic dicarboxylic acids such as dicarboxylic acids are preferred, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid are particularly preferred.
  • terephthalic acid is most preferable from the viewpoint of economy.
  • the illustrated dicarboxylic acids can be used alone or in combination.
  • the melt-blended mixed resin composition is a polymer alloy, in other words, whether or not it is completely compatible, is determined by, for example, a glass transition temperature measured at a heating rate of 10 ° C./min by differential scanning calorimetry. It can be judged by whether it becomes one.
  • the single glass transition temperature of the mixed resin composition means that the glass transition temperature of the mixed resin composition is determined using a differential scanning calorimeter at a heating rate of 10 ° C./min according to JIS K-7121. It means that only one peak indicating the glass transition temperature appears when measured.
  • the mixed resin composition was measured by dynamic viscoelasticity measurement (dynamic viscoelasticity measurement of JIS K-7198A method) at a strain of 0.1% and a frequency of 10 Hz, the loss tangent (tan ⁇ ) was maximized. It can also be determined whether there is one value. If the mixed resin composition is completely compatible (polymer alloying), the blended components are compatible with each other on the nanometer order (molecular level).
  • the mixing ratio of the polycarbonate resin and the polyester d1 or d2 described above is such that the absolute value of the difference in glass transition temperature between the polycarbonate resin composition obtained by mixing and the acrylic resin is within 30 ° C.
  • the thermoplastic resin composition a is mainly composed of an acrylic resin in the example of (3).
  • the thermoplastic resin composition c is a mixture of a polycarbonate resin and a plasticizer will be described in detail.
  • the glass transition temperature of polycarbonate resin is around 150 ° C., which is higher by 50 ° C. than the general glass transition temperature of acrylic resin, which is 50 ° C.
  • a method of reducing the glass transition temperature of the polycarbonate resin by mixing a plasticizer with the latter polycarbonate resin can be mentioned.
  • plasticizer examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate.
  • Phosphate compounds such as 2-ethylhexyl diphenyl phosphate; phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl phthalate), diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate Acid ester compounds; trimellitic acid ester compounds such as tris (2-ethylhexyl) trimellitate; Methyl adipate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisodecyl adipate, bis (butyldiglycol) adipate, bis (2-ethylhexyl)
  • the resin component is a polycarbonate resin
  • a phosphoric acid ester-based compound is preferable because of its good compatibility with the polycarbonate resin and good transparency of the resin after the compatibility.
  • cresyl diphenyl phosphate and tricresyl phosphate are more preferable.
  • thermoplastic resin composition c is a mixture of a polycarbonate resin and a plasticizer
  • the amount of the plasticizer is less than the above-described ratio, the effect of lowering the glass transition temperature due to plasticization becomes insufficient, and the absolute value of the difference in glass transition temperature between the resin layer A and the thermal resin layer C is within 30 ° C. As a result, it may be difficult to improve the thermoformability of the resulting molded resin laminate.
  • the amount of the plasticizer is larger than the above-described ratio, the fluidity of the thermoplastic resin composition c containing the polycarbonate resin is remarkably increased.
  • the molding resin is obtained by coextrusion molding with the thermoplastic resin composition a. When it is set as a laminated body, there exists a possibility that the external appearance may be impaired.
  • the manufacturing method of the molded object concerning this invention is formed from the resin layer C formed from the thermoplastic resin composition c, the resin layer A formed from the thermoplastic resin composition a, and the curable resin composition b.
  • a molding resin laminate obtained by laminating at least three layers of the resin layer B in this order is drawn at a temperature lower than the glass transition temperature of the resin layer A.
  • a method of forming using a forming apparatus such as a press forming machine or a vacuum / pressure forming machine is a preferable example.
  • a forming apparatus such as a press forming machine or a vacuum / pressure forming machine
  • mold in the state which heated the laminated body to the temperature below the glass transition temperature of the resin layer A, and restrict
  • the range of expansion deformation of the resin layer A is limited, and the expansion deformation of the resin layer B laminated on the resin layer A is also suppressed.
  • the extension deformation follows the extension deformation of the layer A, and the laminate can be shaped, and the drawing depth of the molded body can be 1 mm or more and 40 mm or less.
  • the box shape in the present invention is a bottomed container shape, and examples thereof include a cylindrical shape, a rectangular tube shape, a conical shape, a pyramidal shape, a spherical head shape, and a different shape.
  • the in-mold molded body of the present invention is formed by injection molding a molten resin on the resin layer C side of the molded body to form a backing layer.
  • Examples of the technique for obtaining the in-mold molded body include a technique for forming a backing layer by injection molding a molten resin on the resin layer C side of the molded body obtained in advance. That is, after setting the molded body in the injection mold (female mold) that matches the shape and dimensions of the molded body so that the resin layer B side is the female mold surface side, the injection mold (male mold) ) And the molten resin is injected and filled into the clearance between the resin layer C side of the molded body and the injection mold (male mold) to form a backing layer and obtain an in-mold molded body. it can.
  • the molded body has a configuration in which at least three layers of the resin layer C, the resin layer A, and the resin layer B are laminated in this order, but may have a multilayer configuration of four or more layers including other layers.
  • the resin layer D is laminated on the opposite side of the surface on which the resin layer A is laminated, and more specifically, the resin layer D / resin layer C / resin layer A. / Structure of resin layer B and the like.
  • the thickness of the molded body is not particularly limited, and is preferably, for example, 0.1 mm to 1.5 mm. In particular, in consideration of handling in practical use, it is about 0.2 mm to 1.0 mm. preferable.
  • the surface protection panel used by being arranged on the front side of the image display device preferably has a thickness of 0.2 mm to 1.2 mm.
  • a front cover such as a mobile phone having a touch panel function or a liquid crystal pen tablet
  • the material preferably has a thickness of 0.3 mm to 1.0 mm.
  • the roundness (R) of the corner is preferably 2 mm or more and 200 mm or less, more preferably 4 mm or more and 100 mm or less, and particularly preferably 8 mm or more and 50 mm or less. .
  • the curable resin composition b for forming the resin layer B should be selected from a wide range such as an organic or organic / inorganic hybrid hard coat agent. This is preferable because excellent surface hardness can be imparted to the molding resin laminate.
  • the roundness (R) of the corner is 200 mm or less, it is sufficient and preferable to cope with various designs of various electronic devices and apparatuses, for example. Note that “roundness” is synonymous with “curvature radius”.
  • FIG. 1 illustrates the configuration of an embodiment of a molding resin laminate that constitutes the molded body.
  • resin layer C (12), resin layer A (13), and The resin laminated body (11) for molding formed by laminating three layers in the order of the resin layer B (14) is illustrated.
  • FIG. 1 (b) a molding resin laminate having a structure in which a resin layer B (14) is laminated on both surfaces of a laminate comprising a resin layer C (12) and a resin layer A (13). 15) is illustrated.
  • the resin layer B (14) on the resin layer C (12) side may be formed of a curable resin different from the resin layer B (14) on the resin layer A (13) side.
  • FIG. 2 illustrates a molded product that has been drawn into a box shape, which is an embodiment of the molded body.
  • film refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japan) (Industrial standard JIS K-6900), “sheet” generally refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width.
  • sheet generally refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width.
  • sheet is included and the term “sheet” is used. In some cases, “film” is included.
  • X is preferably greater than X” and “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It means “smaller”.
  • X or more when expressed as “X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and “Y or less” (Y is an arbitrary number). ) Includes the meaning of “preferably smaller than Y” unless otherwise specified.
  • Glass transition temperature (Tg) of resin layer, storage elastic modulus The resin layers obtained in Examples and Comparative Examples were subjected to dynamic viscoelasticity measurement according to JIS K-7198A method using the following apparatus, the peak temperature of loss tangent (tan ⁇ ) was read, and the glass transition of the resin layer The temperature (Tg) was used. Further, the storage elastic modulus at (glass transition temperature of the resin layer A ⁇ 20) ° C. was read and used as the storage elastic modulus of the resin layer.
  • Dynamic viscoelasticity measuring apparatus DVB200 (made by IT Measurement Control Co., Ltd.) Distance between chucks: 25mm Distortion: 0.1% Temperature range: -50 ° C to 250 ° C Temperature increase rate: 3 ° C / min
  • the molding resin laminates obtained in the examples and comparative examples were thermoformed using the following molding method.
  • ⁇ Forming method A Molding device: Vacuum / pressure forming machine Laminate preheating temperature: 120 ° C. (However, it indicates the temperature of the laminate when preheated for 20 seconds with an IR heater having a surface temperature of 400 ° C.
  • a sample was prepared by forming a resin layer B-3 having a thickness of 30 ⁇ m with a resin composition b-3 on a 12 ⁇ m polyethylene terephthalate film.
  • the storage modulus was evaluated. The results are shown in Table 1.
  • the concentration of the reactive functional group-containing silica in the resin layer B-3 was 31% by mass.
  • the elongation rate of the laminate and the surface of the resin layer B-3 were evaluated for pencil hardness and scratch resistance. The results are shown in Table 1.
  • thermoforming was performed by molding method A to obtain a rectangular box-shaped molded body 1 in which the resin layer B-3 was disposed on the convex surface side.
  • the molded object external appearance was evaluated. The results are shown in Table 1.
  • the molded product of the present invention of Example 1 has excellent surface hardness with a pencil hardness of 5H or more on the surface of the resin layer B, and has a rounded corner (R ) Was a 14 mm square box shape, and had a beautiful appearance with no cracks or cracks.
  • the molded body of Comparative Example 1 has a pencil hardness on the surface of the resin layer B of 5H or higher, and has an excellent surface hardness. However, cracks and cracks are generated on the surface, and a molded body having an excellent appearance can be obtained. There wasn't.
  • the storage elastic modulus of the resin layer A, resin layer B, and resin layer C constituting the resin laminate A is at a predetermined temperature (I). Since the desired relationship is satisfied, it is assumed that a molded article having excellent surface hardness and a beautiful appearance was obtained. Similarly, the fact that the elongation rate of the molding resin laminate used is within a desired range at a predetermined temperature (II) is also presumed to be a factor for obtaining the molded product of the present invention.
  • the surface protection panel used by being arranged on the front side (viewing side) of the image display device is suitably used for a front cover material such as a mobile phone having a touch panel function, a liquid crystal pen tablet, a vehicle-mounted display, a guide plate or a display plate.
  • Resin laminate for molding 12 Resin layer C 13: Resin layer A 14: Resin layer B

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
PCT/JP2014/050255 2013-01-10 2014-01-09 成形体、およびその製造方法 WO2014109373A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014556444A JPWO2014109373A1 (ja) 2013-01-10 2014-01-09 成形体、およびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013002521 2013-01-10
JP2013-002521 2013-01-10

Publications (1)

Publication Number Publication Date
WO2014109373A1 true WO2014109373A1 (ja) 2014-07-17

Family

ID=51167020

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/050255 WO2014109373A1 (ja) 2013-01-10 2014-01-09 成形体、およびその製造方法

Country Status (3)

Country Link
JP (1) JPWO2014109373A1 (zh)
TW (1) TW201434634A (zh)
WO (1) WO2014109373A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019049704A1 (ja) * 2017-09-06 2019-03-14 三菱瓦斯化学株式会社 高硬度成形用樹脂シートおよびそれを用いた成形品

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007161735A (ja) * 2005-11-17 2007-06-28 Mitsubishi Rayon Co Ltd 熱成形用艶消しアクリル樹脂フィルム状物、熱成形用艶消しアクリル樹脂フィルム状物の製造方法、および、この熱成形用艶消しアクリル樹脂フィルム状物を含む積層体
JP2008265062A (ja) * 2007-04-17 2008-11-06 Mitsubishi Rayon Co Ltd 熱成形用アクリル樹脂フィルムとその製造方法及びこの熱成形用アクリル樹脂フィルムを含む積層体
JP2008273187A (ja) * 2007-03-30 2008-11-13 Dainippon Printing Co Ltd 三次元加工用加飾シート及びそれを用いてなる加飾成形品
JP2012210740A (ja) * 2011-03-30 2012-11-01 Dainippon Printing Co Ltd 真空成形用化粧シート、及び該化粧シートを用いてなる化粧材

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007161735A (ja) * 2005-11-17 2007-06-28 Mitsubishi Rayon Co Ltd 熱成形用艶消しアクリル樹脂フィルム状物、熱成形用艶消しアクリル樹脂フィルム状物の製造方法、および、この熱成形用艶消しアクリル樹脂フィルム状物を含む積層体
JP2008273187A (ja) * 2007-03-30 2008-11-13 Dainippon Printing Co Ltd 三次元加工用加飾シート及びそれを用いてなる加飾成形品
JP2008265062A (ja) * 2007-04-17 2008-11-06 Mitsubishi Rayon Co Ltd 熱成形用アクリル樹脂フィルムとその製造方法及びこの熱成形用アクリル樹脂フィルムを含む積層体
JP2012210740A (ja) * 2011-03-30 2012-11-01 Dainippon Printing Co Ltd 真空成形用化粧シート、及び該化粧シートを用いてなる化粧材

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019049704A1 (ja) * 2017-09-06 2019-03-14 三菱瓦斯化学株式会社 高硬度成形用樹脂シートおよびそれを用いた成形品
CN111051063A (zh) * 2017-09-06 2020-04-21 三菱瓦斯化学株式会社 高硬度成型用树脂片以及使用该树脂片得到的成型品
KR20200050985A (ko) * 2017-09-06 2020-05-12 미츠비시 가스 가가쿠 가부시키가이샤 고경도 성형용 수지 시트 및 그것을 이용한 성형품
JPWO2019049704A1 (ja) * 2017-09-06 2020-10-22 三菱瓦斯化学株式会社 高硬度成形用樹脂シートおよびそれを用いた成形品
US11370206B2 (en) 2017-09-06 2022-06-28 Mitsubishi Gas Chemical Company, Inc. High-hardness molding resin sheet and molded article using same
JP7105784B2 (ja) 2017-09-06 2022-07-25 三菱瓦斯化学株式会社 高硬度成形用樹脂シートおよびそれを用いた成形品
KR102588774B1 (ko) 2017-09-06 2023-10-12 미츠비시 가스 가가쿠 가부시키가이샤 고경도 성형용 수지 시트 및 그것을 이용한 성형품

Also Published As

Publication number Publication date
JPWO2014109373A1 (ja) 2017-01-19
TW201434634A (zh) 2014-09-16

Similar Documents

Publication Publication Date Title
JP6295659B2 (ja) 成形用樹脂積層体、および成形体
KR102159523B1 (ko) 합성 수지 적층체
JP6311229B2 (ja) 成形体の製造方法、および成形体
JP2015104883A (ja) 熱成形体および熱成形体の製造方法
JP6832334B2 (ja) 透明樹脂積層体
JP6680036B2 (ja) 積層体
JP6201404B2 (ja) 耐擦傷性樹脂積層体
JP2015104910A (ja) ポリカーボネート樹脂積層体
JP6295660B2 (ja) 成形用樹脂積層体、および成形体
JP5332274B2 (ja) 艶消し積層フィルム
JP2008188970A (ja) 積層シートおよび積層シート被覆金属板
JP2015104881A (ja) 熱成形体および熱成形体の製造方法
JP2014148165A (ja) 成形体、およびその製造方法
WO2014104334A1 (ja) 成形用樹脂積層体、および成形体
JP2015020288A (ja) 耐擦傷性樹脂積層体
JP2014180807A (ja) 保護フィルム付樹脂積層体
JP6167712B2 (ja) 耐擦傷性樹脂積層体
JP2014205342A (ja) 成形体、およびその製造方法
JP2014237302A (ja) 保護フィルム付成形用樹脂積層体、保護フィルム付成形体、および成形体
JP6787925B2 (ja) 透明樹脂積層体
WO2014109373A1 (ja) 成形体、およびその製造方法
WO2014109372A1 (ja) 成形体、およびその製造方法
WO2005063887A1 (ja) 混合樹脂組成物、該混合樹脂組成物を用いたシートと熱収縮性シート、並びに、該熱収縮性シートを用いた収縮ラベルと包装体
JP2022182828A (ja) カード又はパスポート用樹脂組成物、カード又はパスポート用フィルム、カード、及びパスポート
JP2015103072A (ja) タッチパネルカバー

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14738203

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014556444

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14738203

Country of ref document: EP

Kind code of ref document: A1