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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/06—Copolymers with vinyl aromatic monomers
• • 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
  • B32B2307/554—Wear resistance
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/558—Impact strength, toughness
• • 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
  • B32B2307/584—Scratch resistance
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

• the present invention relates to a laminate comprising a layer containing a methacrylic resin and a layer containing a polycarbonate, which are less likely to warp under high temperature and high humidity and have good impact resistance.
• Methacrylic resin is excellent in transparency, scratch resistance, weather resistance and the like.
• polycarbonate is excellent in impact resistance.
• a laminate comprising a layer containing a methacrylic resin and a layer containing a polycarbonate is excellent in transparency, scratch resistance, weather resistance, impact resistance, etc., and is a wall of a house, furniture, home appliances, electronic equipment, display device. Used for surface members such as
• a methyl methacrylate unit and a methacrylic acid unit an acrylic acid unit, a maleic anhydride unit, an N-substituted or unsubstituted myreimide unit, a glutaric anhydride structural unit, and a glutarimide structural unit are selected.
• a laminate including a layer made of a methacrylic resin having a glass transition temperature of 110 ° C. or higher and a layer made of polycarbonate see Patent Document 1).
• Patent Document 1 Japanese Patent Document 1
• An object of the present invention is to provide a laminate comprising a layer containing a methacrylic resin and a layer made of a polycarbonate, which is less likely to warp under high temperature and high humidity and has good impact resistance.
• the present invention provides 45 to 90% by mass of a methacrylic resin and at least an aromatic vinyl compound represented by the following general formula (a) (hereinafter referred to as “aromatic vinyl compound (a)”).
• a copolymer hereinafter referred to as “SMA resin”
• acid anhydride hereinafter referred to as “acid anhydride (b)”
• a layer composed of a resin layer hereinafter referred to as “resin composition (1)”
• a layer composed of polycarbonate a layer composed of polycarbonate.
• R 1 and R 2 each independently represents a hydrogen atom or an alkyl group.
• R 3 and R 4 each independently represents a hydrogen atom or an alkyl group.
• the laminate of the present invention is less warped under high temperature and high humidity and has good impact resistance.
• the resin composition (1) contains a methacrylic resin and an SMA resin.
• the content of the methacrylic resin in the resin composition (1) is in the range of 45 to 90% by mass, preferably in the range of 65 to 85% by mass, and more preferably in the range of 68 to 82% by mass. .
• the laminate of the present invention has excellent transparency, scratch resistance, weather resistance, etc., and is 90% by mass or less. The occurrence of warpage under high temperature and high humidity can be suppressed.
• the methacrylic resin is a resin containing a structural unit derived from a methacrylic acid ester.
• the methacrylic acid ester include methyl methacrylate (hereinafter referred to as “MMA”), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, Methacrylic acid alkyl esters such as pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cyclohexane methacrylate heptyl, methacrylic acid cycloo
• the content of the structural unit derived from the methacrylic ester in the methacrylic resin is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and only the structural unit derived from the methacrylic ester. Also good.
• the methacrylic resin preferably contains 90% by mass or more of structural units derived from MMA, more preferably 95% by mass or more, and even more preferably 98% by mass or more. Only the structural unit derived from MMA may be used.
• the methacrylic resin may contain a structural unit derived from a monomer other than methacrylic acid ester.
• Such other monomers include methyl acrylate (hereinafter referred to as “MA”), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-acrylate Butyl, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylic Cyclohexyl acid, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethy
• MA ethyl acrylate, n-propyl acrylate, acrylic acid Acrylic esters such as isopropyl, n-butyl acrylate, isobutyl acrylate and tert-butyl acrylate are preferred, MA and ethyl acrylate are more preferred, and MA is most preferred.
• the total content of structural units derived from these other monomers in the methacrylic resin is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less.
• the methacrylic resin can be obtained by polymerizing the above methacrylic acid ester and other monomers as optional components.
• the plurality of types of monomers are mixed to prepare a monomer mixture and then subjected to polymerization.
• radical polymerization is preferably performed by a method such as a bulk polymerization method, a suspension polymerization method, a solution polymerization method, and an emulsion polymerization method from the viewpoint of productivity.
• the weight average molecular weight (hereinafter referred to as “Mw”) of the methacrylic resin is preferably 40,000 to 500,000.
• Mw means the standard polystyrene conversion value measured using a gel perem chromatography (GPC).
• the content of the SMA resin in the resin composition (1) is in the range of 10 to 55% by mass, preferably in the range of 15 to 35% by mass, and more preferably in the range of 18 to 32% by mass. .
• the occurrence of warpage under high temperature and high humidity can be suppressed when the content of the SMA resin in the resin composition (1) is 10% by mass or more, and the resistance is 55% by mass or less. Excellent impact.
• the SMA resin is a copolymer composed of at least a structural unit derived from the aromatic vinyl compound (a) and a structural unit derived from the acid anhydride (b).
• the alkyl groups represented by R 1 and R 2 in the general formula (a) and R 3 and R 4 in the general formula (b) are each independently a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl Group, decyl group, dodecyl group and the like, preferably an alkyl group having 12 or less carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group An al
• R 1 is preferably a hydrogen atom, a methyl group, an ethyl group or a t-butyl group.
• R 2 , R 3 and R 4 are preferably a hydrogen atom, a methyl group and an ethyl group.
• the content of the structural unit derived from the aromatic vinyl compound (a) in the SMA resin is preferably in the range of 50 to 85% by mass, more preferably 65 to 82% by mass, and 68 to 80% by mass. More preferably, it is in the range of%.
• the content is in the range of 50 to 85% by mass, the compatibility between the SMA resin and the methacrylic resin is enhanced, and the resin composition (1) is excellent in transparency.
• aromatic vinyl compound (a) examples include styrene; nuclear alkyl-substituted styrene such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene; ⁇ -methylstyrene , ⁇ -alkyl-substituted styrene such as 4-methyl- ⁇ -methylstyrene; and styrene is preferable from the viewpoint of availability.
• aromatic vinyl compounds (a) may be used individually by 1 type, or may use multiple types together.
• the content of the structural unit derived from the acid anhydride (b) in the SMA resin is preferably in the range of 15 to 40% by mass, more preferably in the range of 18 to 35% by mass, and 20 to 32%. More preferably, it is in the range of mass%.
• the resin composition (1) has excellent heat resistance and transparency.
• Examples of the acid anhydride (b) include maleic anhydride, citraconic anhydride, dimethylmaleic anhydride and the like, and maleic anhydride is preferable from the viewpoint of availability. These acid anhydrides (b) may be used individually by 1 type, or may use multiple types together.
• the SMA resin may have a structural unit derived from a monomer other than the aromatic vinyl compound (a) and the acid anhydride (b).
• Such other monomers include MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, methacrylic acid.
• Heptyl acid 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, benzyl methacrylate, phenyl methacrylate, etc.
• MA ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, te acrylate t-butyl, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate Cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, acrylic Examples include acrylic acid esters such as toluyl acid, benzy
• the content of the structural unit derived from the other monomer in the SMA resin is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.
• the SMA resin can be obtained by polymerizing the above-described aromatic vinyl compound (a), acid anhydride (b), and other monomers as optional components.
• a monomer mixture is usually prepared by mixing the monomers to be used, and then subjected to polymerization.
• radical-polymerize by methods, such as a block polymerization method and a solution polymerization method.
• the Mw of the SMA resin is preferably in the range of 40,000 to 300,000.
• the laminate of the present invention has excellent scratch resistance and impact resistance.
• the resin composition (1) has excellent moldability. It is excellent and the productivity of the laminate of the present invention can be increased.
• the mass ratio of the methacrylic resin and the SMA resin (methacrylic resin / SMA resin) contained in the resin composition (1) is the suppression of the occurrence of warpage of the laminate under high temperature and high humidity, transparency, weather resistance, and impact resistance. In view of the above, it is preferably in the range of 45/55 to 90/10, more preferably in the range of 65/35 to 85/15, and still more preferably in the range of 68/32 to 82/18.
• Resin composition (1) is obtained by mixing the above-mentioned methacrylic resin and SMA resin.
• a melt mixing method or a solution mixing method can be used.
• the melt mixing method for example, using a melt kneader such as a uniaxial or multiaxial kneader, an open roll, a Banbury mixer, a kneader, and the like, under an inert gas atmosphere such as nitrogen gas, argon gas, helium gas, etc. Perform melt-kneading.
• methacrylic resin and SMA resin are dissolved and mixed in an organic solvent such as toluene, tetrahydrofuran, or methyl ethyl ketone.
• the resin composition (1) may contain a polymer other than the methacrylic resin and the SMA resin as long as the effects of the present invention are not impaired.
• examples of such other polymers include polyolefins such as polyethylene and polypropylene, polyamides, polyphenylene sulfide, polyether ether ketone, polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polyacetal, and other thermoplastic resins; phenol resins, melamine resins And thermosetting resins such as silicone resins and epoxy resins. These other polymers may be used individually by 1 type, or may use multiple types together.
• the content of these other polymers in the resin composition (1) is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.
• Resin composition (1) may contain various additives as necessary.
• additives include antioxidants, thermal deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes / pigments, and light diffusing agents.
• the content of these additives can be appropriately set within a range not impairing the effects of the present invention.
• the content of the antioxidant is 0.01 to 1 part by mass with respect to 100 parts by mass of the resin composition (1).
• UV absorber content is 0.01-3 parts by mass
• light stabilizer content is 0.01-3 parts by mass
• lubricant content is 0.01-3 parts by mass
• dye / pigment content Is preferably 0.01 to 3 parts by mass.
• the resin composition (1) contains other polymer and / or additive, it is added when the methacrylic resin and / or SMA resin is polymerized, or added when the methacrylic resin and SMA resin are mixed. Or you may add further, after mixing a methacryl resin and SMA resin.
• the glass transition temperature of the resin composition (1) is preferably in the range of 120 to 160 ° C, more preferably in the range of 130 to 155 ° C, and further preferably in the range of 140 to 150 ° C.
• the glass transition temperature in this specification is a temperature when it measures with the temperature increase rate of 10 degree-C / min using a differential scanning calorimeter, and is calculated by the midpoint method.
• the melt flow rate (hereinafter referred to as “MFR”) of the resin composition (1) is preferably in the range of 1 to 10 g / 10 minutes, more preferably in the range of 1.5 to 7 g / 10 minutes. More preferably, it is 2 to 4 g / 10 minutes. When the MFR is in the range of 1 to 10 g / 10 minutes, the stability of heat-melt molding is good.
• MFR of the resin composition (1) in this specification is a value measured using a melt indexer at a temperature of 230 ° C. and a load of 3.8 kg.
• the polycarbonate used in the laminate of the present invention is preferably obtained by copolymerizing a dihydric phenol and a carbonate precursor.
• dihydric phenol examples include 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl) cyclohexane.
• 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4- Hydroxyphenyl) sulfone and the like, and among them, bisphenol A is preferred.
• These dihydric phenols may be used individually by 1 type, or may use multiple types together.
• carbonate precursor examples include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, and haloformates such as dihaloformate of dihydric phenol. These carbonate precursors may be used individually by 1 type, or may use multiple types together.
• the polycarbonate production method is not particularly limited.
• an interfacial polymerization method in which an aqueous solution of a dihydric phenol and an organic solvent solution of a carbonate precursor are reacted at the interface, a dihydric phenol and a carbonate precursor are reacted at high temperature, reduced pressure, Examples thereof include a transesterification method in which the reaction is performed under solvent conditions.
• the Mw of the polycarbonate is preferably in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 70,000.
• the laminate of the present invention is excellent in impact resistance and heat resistance, and when it is 100,000 or less, the polycarbonate is excellent in molding processability and the production of the laminate of the present invention. Increases sex.
• the polycarbonate may contain other polymers as long as the effects of the present invention are not impaired.
• another polymer the same polymer as the other polymer that may be contained in the resin composition (1) can be used. These other polymers may be used individually by 1 type, or may use multiple types together.
• the content of these other polymers in the polycarbonate is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.
• the polycarbonate may contain various additives as necessary.
• an additive the thing similar to the additive which the above-mentioned resin composition (1) may contain can be used.
• the content of these additives can be appropriately set within a range not impairing the effects of the present invention.
• the content of the antioxidant is 0.01 to 1 part by mass and the content of the ultraviolet absorber is 100 parts by mass of the polycarbonate. 0.01-3 parts by weight, light stabilizer content is 0.01-3 parts by weight, lubricant content is 0.01-3 parts by weight, dye / pigment content is 0.01-3 parts by weight Is preferred.
• polymers and / or additives When other polymers and / or additives are added to the polycarbonate, they may be added when copolymerizing the dihydric phenol and the carbonate precursor, or added and melted after the copolymerization is completed. You may knead.
• the glass transition temperature of the polycarbonate is preferably in the range of 130 to 160 ° C, more preferably in the range of 135 to 155 ° C, and still more preferably in the range of 140 to 150 ° C.
• the glass transition temperature is in the range of 130 to 160 ° C., the occurrence of warpage of the laminate of the present invention under high temperature and high humidity can be suppressed.
• the MFR of the polycarbonate is preferably in the range of 1 to 30 g / 10 minutes, more preferably in the range of 3 to 20 g / 10 minutes, and still more preferably in the range of 5 to 10 g / 10 minutes.
• the MFR is in the range of 1 to 30 g / 10 min, the stability of heat-melt molding is good.
• the MFR of polycarbonate in the present specification is measured using a melt indexer under conditions of a temperature of 300 ° C. and a load of 1.2 kg.
• polycarbonate Commercially available products may be used as the polycarbonate.
• “Taflon (registered trademark)” manufactured by Teijin Chemicals Ltd. and “Panlite (registered trademark)” manufactured by Teijin Chemicals Ltd. can be suitably used.
• the laminate of the present invention may have a plurality of layers made of the resin composition (1) and / or layers made of polycarbonate.
• the laminate of the present invention may have a layer made of another resin (another resin layer) in addition to the layer made of the resin composition (1) and the layer made of polycarbonate.
• another resin another resin layer
• the resin contained in the other resin layer include various thermoplastic resins other than the resin composition (1) and polycarbonate; thermosetting resin; energy ray curable resin; and the like.
• Examples of other resin layers described above include a scratch-resistant layer, an antistatic layer, an antifouling layer, a friction reducing layer, an antiglare layer, an antireflection layer, an adhesive layer, and an impact strength imparting layer.
• These other resin layers may be one layer or plural. When there are a plurality of these other resin layers, they may be made of the same resin or different resins. In the laminate of the present invention, the arrangement order of the other resin layers is not particularly limited, and may be the surface or the inner layer.
• the thickness of the laminate of the present invention is preferably in the range of 0.03 to 5.0 mm, and preferably 0.05 to 4.0 mm from the viewpoint of manufacturing with good productivity while maintaining an excellent appearance. Is more preferable, and a range of 0.1 to 3.0 mm is more preferable.
• the thickness of the layer comprising the resin composition (1) in the laminate of the present invention is preferably in the range of 0.01 to 0.5 mm, more preferably in the range of 0.015 to 0.3 mm. More preferably, it is in the range of 0.02 to 0.1 mm. When the thickness is less than 0.01 mm, scratch resistance and weather resistance may be insufficient. If it exceeds 0.5 mm, the impact resistance may be insufficient.
• the thickness of the polycarbonate layer in the laminate of the present invention is preferably in the range of 0.02 to 4.9 mm, more preferably in the range of 0.035 to 3.9 mm, and 0.08 to 2 More preferably, it is in the range of .9 mm. If the thickness is less than 0.02 mm, the impact resistance may be insufficient. Moreover, when it exceeds 4.9 mm, productivity may fall.
• the layer composed of the resin composition (1) is represented as (1), and the layer composed of polycarbonate as (2).
• the stacking order of the laminate of the present invention is as follows: (1)-(2); (1)-(2)-(1); (2)-(1)-(2); (1)-(2 )-(1)-(2)-(1); and the like, and (1)-(2); (1)-(2)-(1); (1) from the viewpoint of enhancing the scratch resistance -(2)-(1)-(2)-(1); etc. are preferably laminated so that at least one surface is a layer made of the resin composition (1).
• the stacking order of the laminate of the present invention is (1)-(2) -(3); (3)-(1)-(2); (3)-(1)-(2)-(3); (3)-(1)-(2)-(1)-( 3); (1)-(2)-(3)-(2)-(1);
• the stacking order of the laminate of the present invention is (3 ′)-(1)-(2); At least one surface such as 3 ′)-(1)-(2)-(3 ′), (3 ′)-(1)-(2)-(1)-(3 ′) is a scratch-resistant layer It is preferable that they are laminated.
• the stacking order of the laminate of the present invention is (1)-(2)-(3)-(4); (4)-(3)-(1)-(2); (4)-( 3)-(1)-(2)-(3); (4)-(1)-(2)-(3); (4)-(3)-(1)-(2)-(3) -(4); (4)-(3)-(1)-(2)-(1)-(3)-(4);
• the antireflection layer is expressed as (4 ′), and (4 ′) ⁇ (3 ′) ⁇ (1) ⁇ ( 2); (4 ')-(3')-(1)-(2)-(3 '); (4')-(3 ')-(1)-(2)-(3')-( 4 ′); (4 ′)-(3 ′)-(1)-(2)-(1)-(3 ′)-(4 ′);
• the laminate of the present invention has a lamination order that is symmetrical in the thickness direction, and that the thickness of each layer is also symmetrical. preferable.
• the production method of the laminate of the present invention is not particularly limited, but the lamination of the layer made of the resin composition (1) and the layer made of polycarbonate is usually preferably performed by multilayer molding.
• multilayer molding include multi-layer extrusion molding, multilayer blow molding, multilayer press molding, multicolor injection molding, insert injection molding and the like, and multilayer extrusion molding is preferred from the viewpoint of productivity.
• a method for further laminating other resin layers a method of multilayer molding by the above-described method together with a layer made of the resin composition (1) and a layer made of polycarbonate, a layer made of the resin composition (1) prepared beforehand or a polycarbonate
• the method of multilayer extrusion molding is not particularly limited, and a known multilayer extrusion molding method used for the production of multilayer laminates of thermoplastic resins can be preferably employed, and more preferably a flat T die and a surface with a mirror-finished polishing. Molded by an apparatus equipped with a roll.
• the T-die method is a feed block method in which the resin composition (1) and polycarbonate in a heated and melted state are laminated before inflow of the T-die, and the resin composition (1) and polycarbonate are laminated inside the T-die.
• a multi-manifold system can be used. From the viewpoint of improving the smoothness of the interface between the layers constituting the laminate, the multi-manifold method is preferable.
• Resin composition (1) and polycarbonate are preferably melt filtered through a filter before multilayer molding.
• the filter medium used is not particularly limited, and is appropriately selected depending on the operating temperature, viscosity, and filtration accuracy.
• nonwoven fabric made of polypropylene, cotton, polyester, rayon, glass fiber, etc .; phenol resin-impregnated cellulose film; Bonded film; metal powder sintered film; wire mesh; or a combination thereof.
• the filtration accuracy of the filter is not particularly limited, but is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
• the scratch-resistant layer will be described in detail as an example of a layer made of another resin composition.
• the scratch-resistant layer means a layer having a hardness of “3H” or higher in a pencil scratch test specified by JIS-K5600-5-4. A layer having a hardness of “4H” or more is preferable.
• the scratch-resistant layer is preferably provided on the surface of the layer made of the resin composition (1).
• the thickness of the scratch-resistant layer is preferably 2 to 10 ⁇ m, more preferably 3 to 8 ⁇ m, still more preferably 4 to 7 ⁇ m.
• the thickness is 2 ⁇ m or more, scratch resistance tends to be maintained, and when the thickness is 10 ⁇ m or less, the impact resistance of the laminate tends to be excellent.
• the scratch-resistant layer is usually obtained by applying a fluid curable composition comprising a monomer, oligomer, resin, etc. to the surface of another layer (for example, a layer comprising a resin composition (1) or a layer comprising a polycarbonate) It can be formed by curing.
• a fluid curable composition comprising a monomer, oligomer, resin, etc.
• another layer for example, a layer comprising a resin composition (1) or a layer comprising a polycarbonate
• curable compositions are, for example, thermosetting compositions that are cured by heat and energy beam curable compositions that are cured by energy beams such as electron beams, radiation, and ultraviolet rays.
• thermosetting composition examples include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon
• thermosetting compositions may contain, for example, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, and the like as necessary.
• isocyanate organic sulfonic acid and the like are usually used for polyester resins and polyurethane resins
• amine is epoxy resin, peroxide such as methyl ethyl ketone peroxide, radical initiator such as azobisisobutyl ester. Used for unsaturated polyester resins.
• the energy ray curable composition examples include a composition containing an oligomer and / or a monomer having a polymerizable unsaturated bond such as an acryloyl group or a methacryloyl group, a thiol group, or an epoxy group in the molecule. From the viewpoint of enhancing the scratch resistance, a composition containing an oligomer and / or monomer having a plurality of acryloyl groups or methacryloyl groups is preferred.
• the energy beam curable composition may contain a photopolymerization initiator and / or a photosensitizer.
• photopolymerization initiators include carbonyl compounds such as benzoin methyl ether, acetophenone, 3-methylacetophenone, benzophenone and 4-chlorobenzophenone; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; -Trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide and the like, and photosensitizers include n-butylamine, triethylamine, tri-n-butylphosphine and the like.
• the content of these curable compounds is preferably in the range of 30 to 100% by mass, more preferably in the range of 40 to 95% by mass, and in the range of 50 to 95% by mass. More preferably it is.
• These curable compounds may be used alone or in combination of two or more.
• the curable composition may be a monofunctional monomer; an organic solvent; a leveling agent, an antiblocking agent, a dispersion stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an antifoaming agent, a thickener, if necessary.
• An additive such as a lubricant, an antistatic agent, an antifouling agent, an antifogging agent, a filler, and a catalyst may be appropriately contained. The content of these additives can be appropriately set as long as the effects of the present invention are not impaired.
• Examples of the coating method for the curable composition include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, and screen printing. Is mentioned.
• the test piece produced from the laminated body obtained by the Example and the comparative example it fixed so that the base and the layer which consists of a polycarbonate might oppose.
• a steel ball having a diameter of 30 mm and a mass of 112 g was freely dropped from the vertical height of 10 cm at the center of the test piece, and the presence or absence of appearance changes such as dents, cracks, fractures, cloudiness, and whitening was observed with the naked eye.
• the height at which the steel ball is allowed to freely fall is increased by 10 cm, and the same observation is repeated.
• the height at which the appearance change is made ⁇ 10 cm, that is, the highest height at which the appearance change has not occurred is determined as the impact resistance. Recorded as an indicator.
• Total light transmittance The laminates of Examples and Comparative Examples were measured using a spectral color difference meter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. according to the method described in JIS-K7361.
• both ends of the test piece having such bow-shaped warpage are in contact with the surface plate (that is, the test piece has an upward convex shape, and the layer made of the resin composition (1) is made of polycarbonate on the upper side.
• the maximum value of the gap between the test piece and the surface plate was measured using a gap gauge, the value was taken as the initial amount of warpage.
• a test piece having a short side fixed with a clip was suspended in an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85%, and left in that state for 24 hours.
• resin composition (1-1) a pellet-shaped resin composition
• the composition is shown in Table 1.
• the MFR of the resin composition (1-1) measured with a melt indexer at a temperature of 230 ° C. and a load of 3.8 kg was 3.2 g / 10 min.
• the polymerization reaction liquid was cooled to room temperature, solid content was separated by filtration, washed with water, and dried in hot air at 80 ° C. for 24 hours.
• the solid content was supplied to a hopper of a twin screw extruder, melt kneaded at a cylinder temperature of 230 ° C., and extrusion molded to obtain a pellet-shaped methacrylic resin (hereinafter referred to as “methacrylic resin (X)”).
• the resin composition is shown in Table 2.
• the MFR of the methacrylic resin (X) measured under a load of 3.8 kg at a temperature of 230 ° C. using a melt indexer was 2.1 g / 10 min.
• pellets of the resin composition (1-1) were continuously charged into a single screw extruder having a shaft diameter of 30 mm, and extruded in a molten state under conditions of a cylinder temperature of 220 ° C. and a discharge rate of 2 kg / hour.
• the molten polycarbonate and the resin composition (1-1) are introduced into a junction block, laminated with a multi-manifold die set to 250 ° C., extruded into a sheet, and a resin composition (1- A laminate having a thickness of 1000 ⁇ m formed from two layers of a layer consisting of 1) and a layer consisting of a polycarbonate having a thickness of 940 ⁇ m was produced.
• Table 3 shows the evaluation results of the laminate.
• Example 2 A laminate was produced in the same manner as in Example 1 except that the resin composition (1-2) was used instead of the resin composition (1-1) in Example 1. Table 3 shows the evaluation results of the laminate.
• Example 3 A laminate was produced in the same manner as in Example 1, except that the resin composition (1-3) was used instead of the resin composition (1-1) in Example 1. Table 3 shows the evaluation results of the laminate.
• Example 4 A laminate was produced in the same manner as in Example 1 except that the resin composition (1-4) was used instead of the resin composition (1-1) of Example 1. Table 3 shows the evaluation results of the laminate.
• Example 1 A laminate was produced in the same manner as in Example 1 except that the methacrylic resin (A) was used instead of the resin composition (1-1) in Example 1. Table 3 shows the evaluation results of the laminate.
• Example 2 A laminate was produced in the same manner as in Example 1 except that the resin composition (1 ′) was used instead of the resin composition (1-1) of Example 1. Table 3 shows the evaluation results of the laminate.
• Example 3 A laminate was produced in the same manner as in Example 1 except that the methacrylic resin (X) was used instead of the resin composition (1-1) in Example 1. Table 3 shows the evaluation results of the laminate.
• Sheets (Reference Examples 1 to 4, 6) made of the resin composition (1) or the resin composition (1 ′) used in the laminate of the present invention are sheets made of a methacrylic resin (X) copolymerized with TCDMA (reference) Similar to Example 7), the glass transition temperature is higher and the saturated water absorption is lower than that of the sheet made of methacrylic resin (A) (Reference Example 5). It is presumed that the high glass transition temperature and low saturated water absorption rate of the sheet made of the resin composition (1) are caused by the suppression of the occurrence of warpage of the laminate of the present invention under high temperature and high humidity.
• the sheets (Reference Examples 1 to 4 and 6) made of the resin composition (1) or (1 ′) are made of the methacrylic resin (A) in the same manner as the sheets made of the methacrylic resin (X) (Reference Example 7).
• the impact resistance is reduced as compared with the sheet (Reference Example 5).
• a laminate using a methacrylic resin (A) which is a general methacrylic resin instead of the resin composition (1) (Comparative Example) Compared with 1), the amount of change in warping is significantly less, and the impact resistance is hardly lowered.
• the laminate of the present invention can improve the amount of change in warpage without degrading various performances of the conventional laminate of methacrylic resin (A) and polycarbonate.
• the laminate of the present invention is characterized in that it is less likely to warp under high temperature and high humidity and has excellent impact resistance, and is suitable for use on the surface of a display device or the like.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Extrusion Moulding Of Plastics Or The Like (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (1)

Applications Claiming Priority (4)

Publications (1)

Family

ID=52778642

Family Applications (1)

Country Status (3)

Cited By (8)

Citations (4)

Family Cites Families (1)

• 2014
  • 2014-09-26 JP JP2015540469A patent/JP6430950B2/ja active Active
  • 2014-09-26 WO PCT/JP2014/075604 patent/WO2015050051A1/ja active Application Filing
  • 2014-10-01 TW TW103134153A patent/TWI643748B/zh active

Patent Citations (4)

Also Published As

Similar Documents

Legal Events