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WO1997046383A1 - Plaque stratifiee multicouche coextrudee et procede de confection d'objet moule en plastique utilisant une telle plaque - Google Patents

Plaque stratifiee multicouche coextrudee et procede de confection d'objet moule en plastique utilisant une telle plaque Download PDF

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Publication number
WO1997046383A1
WO1997046383A1 PCT/JP1997/001908 JP9701908W WO9746383A1 WO 1997046383 A1 WO1997046383 A1 WO 1997046383A1 JP 9701908 W JP9701908 W JP 9701908W WO 9746383 A1 WO9746383 A1 WO 9746383A1
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WIPO (PCT)
Prior art keywords
layer
group
modified
thermoplastic
polymer
Prior art date
Application number
PCT/JP1997/001908
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English (en)
Japanese (ja)
Inventor
Izumi Ishii
Hitoshi Yamada
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Mitsubishi Chemical Corporation
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Publication date
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Publication of WO1997046383A1 publication Critical patent/WO1997046383A1/fr

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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
    • B32B27/06—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
    • 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
    • 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
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • 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
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/002—Coloured

Definitions

  • the present invention can provide a coextruded multilayer laminated sheet having a specific layer configuration and excellent in gloss and color, and by using the same, can omit the use of a paint application and casting sheet.
  • the present invention relates to a method for manufacturing a plastic fi ⁇ body, and particularly to a method for manufacturing an automobile exterior component.
  • this method uses volatile organic ⁇ PJ in the process of manufacturing the composite paint coat, so that the P problem of environmental protection has not been sufficiently solved, and several steps of coating are performed on a casting sheet. Or also casting It requires a step of peeling off the sheet, and has the disadvantage that it is complicated. In addition, this method cannot make the transparent layer, the expansion layer, and the adhesive layer sufficiently thick. Therefore, when manufacturing a molded article such as an automobile exterior member that is complicated and has a large expansion ratio due to shape, it is a final recommendation. Necessary adhesion between layers 3 ⁇ 4Jg force ⁇ cannot be obtained ⁇ There were problems such as uneven gloss and uneven color.
  • An object of the present invention is to improve the disadvantages of the prior art, eliminate the need for a coating step and eliminate the use of a casting sheet, and provide a co-extruded metal, sheet and sheet having excellent light and color. It is an object of the present invention to provide a method for producing a plastic molded product, particularly an automobile exterior member.
  • the present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the above-described objective power 3 ⁇ 41 ⁇ has been obtained by using a co-extruded multilayer 3 ⁇ 4s sheet having a specific layer configuration and by forming this sheet.
  • the present invention has been found.
  • one of the present invention is a thermoplastic acrylic polymer containing a ⁇ agent and
  • a colored layer (A) composed of Z or a thermoplastic resin, an employment of a modified olefin polymer containing at least one kind of t! S selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group and a glycidyl group.
  • a co-extruded multilayer sheet characterized in that (B) and a back-up layer (C) comprising an olefin polymer are laminated in the order of (A) / (B) / (C).
  • Another aspect of the present invention is to provide a colored layer (A) comprising a thermoplastic acryl-based polymer and / or a thermoplastic fluororesin containing a colorant, a carboxyl group, a hydrate group, a hydroxyl group and a glycidyl group.
  • (B) comprising at least one modified S-containing olefin polymer selected from the group consisting of: and a backup layer comprising the olefin polymer
  • thermoplastic acrylic polymer and / or the thermoplastic fluororesin constituting the layer (A) is at least one kind selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group and a glycidyl group.
  • a modified thermoplastic acryl-based polymer containing 1% of food and Z or a modified thermoplastic fluororesin are preferred in view of further increasing the durability of adhesion.
  • the transparent layer (T) made of an organic or inorganic compound having an excess ratio of 75 is further provided on the surface of the layer (A) is advantageous in that the color depth of the co-extruded multilayer ⁇ ⁇ ⁇ ⁇ sheet surface is further increased. Is preferred.
  • the conjugated material constituting the layer (T) is preferably a thermoplastic acrylic polymer and / or a thermoplastic fluorinated resin, and is preferred in terms of its formability.
  • the plastic body is an automobile exterior member, a particularly large effect can be expected.
  • the layer (A) which is one of the constituent layers of the co-extruded multilayer laminated sheet of the present invention, is a fiber blended with a coloring agent (eg, a pigment) commonly used in thermoplastic acrylic polymers and / or thermoplastic resins.
  • a coloring agent eg, a pigment
  • thermoplastic acrylic polymer include, for example, atarilic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, There are homopolymers such as acrylonitrile and methacrylonitrile, and copolymers containing these as main components. Specific examples include polymethyl acrylate, methyl methacrylate-methyl acrylate copolymer, and methyl methacrylate-ethyl acrylate copolymer.
  • methyl methacrylate-ethyl methacrylate copolymer In addition to polymers, methyl methacrylate-ethyl methacrylate copolymer, polyacrylonitrile, acrylonitrile-methyl methacrylate copolymer, etc., as well as acrylonitrile and / or ⁇ or methacrylic acid ester for rubbery polymers Graft copolymers are listed in the official gazettes of Japanese Patent Publication No. 49-146, 58, 49-461, 59, 50-90 22 and 60-233 35 Impact-resistant acryl-based polymers obtained by such multi-stage polymerization can be exemplified. Above all, a homopolymer of methyl methacrylate or acrylonitrile or a copolymer containing these as components is preferable.
  • thermoplastic acrylic polymers are not excluded from being blended with other polymers such as polyvinylidene fluoride, polycarbonate, and the like, as long as the coloring properties, physical properties, and moldability are not significantly impaired. Further, two or more resins can be used in combination.
  • thermoplastic resin examples include, for example, polyvinyl fluoride, polyvinylidene fluoride, polychloroethylene trifluorethylene, ethylene-tetrafluoroethylene copolymer, ethylene monochlorotrifluoroethylene copolymer, Commercial products such as tetrafluoroethylene-ethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene-pyrene copolymer, and tetrafluoroethylene-perfluoroalkylvinyl ether copolymer are available. Although used appropriately, polyvinyl fluoride and polyvinylidene vinylidene are particularly preferred. It should be noted that these thermoplastic fluororesins do not exclude other polymers such as polymethyl methacrylate and additives, for example, as long as their properties and impact resistance are not significantly impaired. Also, two or more resins can be used together.
  • colorants include azo pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, perylene pigments, perinone pigments, and dioxazines. And organic pigments such as quinophthalone pigments; and inorganic pigments such as titanium oxide, red iron oxide, ultramarine, graphite, chromium permillion, and complex oxide pigments.
  • the amount of the colorant to be added to the thermoplastic acryl-based polymer and / or the thermoplastic resin is usually 0.1 to 20 Mfi%, preferably 0.1 to 20 Mfi%, from the viewpoint of the design property and the polymer content. 5 to 10 times; S%.
  • thermoplastic acrylic polymer and Z or the thermoplastic fluororesin constituting the layer (A) may be modified in the layer (D) described below in order to further increase the durability of the adhesive strength. It is preferable to use a thermoplastic acryl-based polymer and Z or a modified thermoplastic fluororesin.
  • the modification is carried out by a method of blending a thermoplastic polymer having compatibility with a thermoplastic acrylic polymer and / or a thermoplastic fluororesin and having a functional group. .
  • the layer (B), which is one constituent layer of the co-extruded multilayer laminated sheet of the present invention, is a modified olefin polymer containing at least one functional group selected from a carboxy group, an acid anhydride group, water and a glycidyl group. It consists of Here, the homopolymer of ⁇ -olefin such as ethylene, propylene, butene, pentene, hexene, octene, decene, 3-methylbutene, 4-methylpentene, etc.
  • these ⁇ -olefins are separated into blocks, random or graphitic copolymers based on other heavy monomers (for example, diolefins, unsaturated carboxylic acids are derivatives, vinyl esters, aromatic vinyls, etc.). Coalescing is preferably used.
  • these olefin polymers are combined with other compatible polymers, additives, fillers, pigments, and the like. .
  • two or more of these polymers can be used in combination.
  • the methods (1) and (2) are most preferable because they do not impair the physical properties of the polymer.
  • the heavy monomer having a functional group may be a carboxyl group or an acid anhydride group, such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid.
  • hymic acid (3,6-endmethylenetetrahydrophthalic acid) or their anhydrides (among them, acrylic acid and maleic anhydride are preferred in terms of adhesiveness).
  • the functional group is a hydroxyl group
  • vinyl ester polymers such as vinyl acetate, vinyl polypropionate, and ethylene monoacetate
  • unsaturated carboxylic acids such as acrylic acid and methacrylic acid
  • divalent alcohols There are unsaturated alcohol polymers and the like, in which unsaturated alcohols such as monoesters with polyesters are homopolymerized or copolymerized with other heavy monomers
  • unsaturated alcohols such as monoesters with polyesters are homopolymerized or copolymerized with other heavy monomers
  • the glycidyl group is a dalicidyl group, for example, glycidyl acrylate, glycidyl methacrylate And glycidyl ethyl acrylate, glycidyl itaconate, and the like (of which glycidyl acrylate is preferable in terms of reactivity).
  • the content of the functional group is required to be at least 0.001 mol Z 100 g from the viewpoint of adhesiveness.
  • Physical properties such as impact strength and rigidity balance, and compatibility with the same type of unmodified resin
  • a force of less than 0.3 mol / 100 g is preferred, and among them, 0.05 to 0.2 mol Z 100 £, particularly 0.01 to 1 mol / ⁇ 100 g is preferred.
  • the modified olefin polymer contains 2 to 60 (particularly 5 to 50)% by weight of an amorphous rubbery polymer. This is preferable because the adhesiveness with the thermoplastic acryl-based polymer and / or the thermoplastic fluororesin is improved.
  • rubbery polymers include ethylene copolymers such as ethylene-propylene copolymer rubber, ethylene-propylene-gen copolymer rubber, ethylene-butene-11 copolymer rubber, and propylene-butene-11 copolymer rubber.
  • the olefin copolymer rubber is preferably used from the viewpoint of improving compatibility with the modified olefin polymer and adhesion.
  • the modified olefin polymer may further contain other thermoplastic polymers such as polyamides and polyesters, as long as the adhesiveness, physical properties, and the like are not significantly impaired.
  • the olefin polymer can be appropriately selected from the olefin polymers used for modification in the above-mentioned modified olefin polymer, and among them, a crystalline resin-like one is particularly preferable.
  • Better No. Preferred types are ethylene polymer resin and propylene polymer resin.
  • the addition of other polymers, additives, fillers and the like is not excluded for the olefin polymer. Further, two or more of these polymers can be used in combination.
  • a carboxyl group, a hydrate group, a 7_R acid group and a glycidyl group are added between the above-mentioned layer (A) and layer (B) of the co-extruded multilayer laminated sheet of the present invention in order to further increase the durability of the adhesive strength. It is preferable to further laminate a layer (D) comprising a modified thermoplastic acryl-based polymer containing at least one member selected from the group consisting of Z and Z or a modified thermoplastic resin.
  • the thermoplastic acrylic polymer and Z or the thermoplastic fluororesin used for the modification the thermoplastic acryl-based polymer and / or the thermoplastic resin described as constituting the layer (A) are used. It can be used properly from among them.
  • thermoplastic acrylic polymers and fluorinated or thermoplastic fluororesins do not include other polymers or additives unless they are significantly impaired in transparency, moldability or impact resistance. do not do.
  • two or more resins can be used in combination.
  • polyvinylidene fluoride, polycarbonate, or the like can be mixed with a thermoplastic acrylic polymer, or polymethyl methacrylate or the like can be mixed with a thermoplastic resin.
  • thermoplastic acryl-based polymer and / or thermoplastic resin As a method for modifying the thermoplastic acryl-based polymer and / or thermoplastic resin by adding the above functional group to the thermoplastic resin,
  • thermoplastic polymer having compatibility with a thermoplastic acrylic polymer and / or a thermoplastic fluororesin, and having a functional group and a functional group
  • the method (1) is the most convenient and preferable.
  • the thermoplastic polymer having compatibility with the thermoplastic acrylic polymer and / or the thermoplastic resin and having a good quality is preferably a carboxyl group or an acid anhydride.
  • acrylic acid methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, methacrylonitrile, etc. containing at least one kind selected from the group consisting of Can be used.
  • polyacrylic acid polymethacrylic acid, methyl methacrylic acid-methacrylic acid ⁇ copolymer, methyl methacrylate-monoacrylic acid copolymer, methyl methacrylate-methacrylic acid copolymer, hydroxyethyl ethyl polyacrylate, poly Hydroxyethyl methacrylate, acrylate-hydroxyethyl acrylate copolymer, acrylate-hydroxyethyl methacrylate copolymer, methacrylate-hydroxyethyl acrylate copolymer, methyl methacrylate-hydroxyethyl methacrylate copolymer Glycidyl polyacrylate, polyglycidyl methacrylate, glycidyl acrylate / glycidyl acrylate copolymer, acrylate-glycidyl methacrylate copolymer, methyl methacrylate-glycidyl methacrylate copolymer
  • the heavy monomer having When 3 ⁇ 4 is a carboxyl group or an acid anhydride group there are, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, hymic acid or anhydrides thereof (among others, acrylolic acid in terms of adhesiveness). And maleic acid are preferred).
  • the IS is a hydroxyl group
  • acrylates of vinyl ester polymers such as polyvinyl vinyl succinate, polyvinyl propionate, and ethylene-vinyl acetate copolymer
  • unsaturated acids such as acrylic acid and methacrylic acid
  • An unsaturated alcohol polymer obtained by homopolymerizing an unsaturated alcohol such as a monoester of a carboxylic acid and a dihydric alcohol or copolymerizing with another heavy ft monomer is also available.
  • the thigh is a glycidyl group
  • examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethyl acrylate, and glycidyl itaconate (among them, glycidyl acrylate is preferred in terms of reactivity).
  • the heavy acryl-based monomer a heavy acryl-based monomer which is a unit capable of constituting a thermoplastic acryl-based polymer can be used.
  • the deuterium-fluorine-containing monomer a suitable one can be selected from deuterium-fluorine-containing monomers, which are units capable of constituting a thermoplastic fluororesin.
  • the content of the functional group contained therein is determined from the viewpoint of adhesiveness.
  • 0.1 g / 100 g or more is required.
  • physical properties such as impact resistance—rigidity balance, and compatibility with the same type of unmodified resin, 0.3 mol / g It is preferably less than 100 g and more preferably 0.005 to 0.2 mol 100 g, particularly preferably 0.01 to 0.1 mol / 100 g.
  • the transparent coating (T) which may be further provided on the surface of the above-mentioned footwear (A) of the co-extruded multilayer laminated sheet of the present invention is a layer comprising an inorganic compound having a transmittance of 75% or more. is there. Providing a transparent exhibition (cho) increases the color depth of the coextruded multi-expanded laminated sheet surface. It is preferable from the viewpoint of further addition.
  • examples of the organic compound include thermoplastic acrylic polymer, thermoplastic fluororesin, polycarbonate, polystyrene, diethylene glycol bisarylcarbonate resin, polyvinyl chloride, acrylonitrile-styrene copolymer resin, and styrene-methyl methacrylate copolymer.
  • polymer resin polycyclohexyl methacrylate, poly-4-methylpentene-11, etc., JP-A-61-27308, 61-272, 216, 61 —A copolymer resin of ethylene and cyclic olefin described in each of the publications can be used.
  • mineralization ⁇ ! For example, silica can be mentioned.
  • a method of laminating the inorganic compound a method of co-extrusion of an inorganic compound and the above-mentioned polymer, which is previously melted and pelletized, and a method such as vapor deposition, sputtering, and coating are used.
  • ItX is a thermoplastic acryl-based polymer and / or a thermoplastic fluorinated fat among inorganic compounds in terms of thermal ⁇ -property, and in particular, a m-polymer of methyl methacrylate or acrylonitrile or these.
  • the main copolymer, polyvinyl fluoride, and polyvinylidene fluoride are preferred.
  • these thermoplastic acrylic polymers and / or thermoplastic resins are not excluded from being combined with other polymers or additives unless the transparency, moldability or impact resistance is significantly impaired.
  • two or more resins can be used in combination.
  • polyvinylidene fluoride, polycarbonate, and the like can be blended with a thermoplastic acryl-based polymer, and polymethyl methacrylate and the like can be blended with a thermoplastic resin.
  • the above (A) z layer (B) / layer (c) and layer (A) / m (D) are formed by co-extrusion using the material constituting each layer described above. / m (B)
  • the material constituting each layer should be intense, with the melting point of the material brass lower than 80 ° C.
  • the layer (A) which is a colored layer, is preferably in the range of 50 to 500 m in order to create a color required for an exterior member of an automobile, and particularly preferably 50 to 400 m. ⁇ m is particularly preferred.
  • Layer (B) and layer (D) are each preferably in the range of 5 to 300 to obtain the required adhesion between the colored layer and the backup layer, and are preferably 30 to 300 m. Is particularly preferred.
  • the layer (C) serving as the backup layer preferably has a thickness in the range of 100 to 100 zm in order to suppress breakage due to the shape of the ⁇ f® sheet described later and the injection pressure at the time of injection. .
  • the layer (T) is preferably in the range of 5 to 200 in order to provide the color depth of the sheet surface required for an automobile exterior member.
  • each layer of the co-extruded multilayer laminate sheet is preferably determined in consideration of the expansion ratio described later. More specifically, in the case of the shape: ⁇ crisp! ⁇ Shape, the thickness of each layer is set to be slightly thicker within the range of the thickness of each layer described above.
  • the laminated sheet thus obtained is then formed into a preliminary 5 ⁇ -body having a three-dimensional shape.
  • a means such as a true ⁇ pressure ⁇ , a true E2 ⁇ type, etc. is preferably employed.
  • true ⁇ for example, the above-mentioned co-extrusion multi-layer sheet is used with far-infrared ceramic heaters from both sides. After heating, the mold is moved up, down, left and right, a part of the heated laminated sheet is brought into contact with the mold, and the air generated between the laminated sheet and the mold is evacuated to form a vacuum.
  • a method in which the surface is brought into close contact with a mold, shaped, and cooled and solidified by a forced cooling method using a fan, a blower or the like is preferable.
  • the surface of the laminated sheet at the time of evacuation is in the range of 'ag: Lt lower than the melting point of the resin or polymer constituting each layer by 5 ° C and' a ° 'higher than the melting point by 5 ° C. It is preferable that
  • These processes include a batch process and a continuous process.
  • a part of the laminated sheet is brought into contact with the mold before it is brought into contact with the mold. It is preferable that a step of spraying ⁇ from the direction to move the mold while inflating the Ml heat sheet into a hemispherical shape and bringing " ⁇ " of the recruitment sheet into contact with the mold is added to the upper part.
  • injection is performed on a hard, high-gloss, highly polished surface that has the same shape as the preform obtained by IWing the coextruded multilayer laminated sheet as described above, and that has no surface defects.
  • the mold is closed, and a space is formed for injecting the ⁇ -olefin polymer ⁇ in contact with the backup of the preform, This is carried out by injecting the olefin polymer into the space so as not to come into contact with the ⁇ f-side transparent film ⁇ of the backup layer.
  • a crystalline resinous material is particularly preferable because it can be appropriately selected from the olefin polymers used in the backup layer and can be used.
  • Preferred are ethylene polymer resin and propylene polymer resin. It should be noted that, as long as the physical properties and male properties are not hindered, the olefin polymer is not required to be blended with other polymers, additives and filling power. In addition, two or more of these polymers may be used in combination.
  • This injection molding is carried out using a conventional injection molding machine at an i® temperature of 180 to 250, preferably 200 to 230 ° C, 100 to 2000 kg / cm 2 , preferably 500 to 1500. 2 / (:. 111 takes place in the second emission output further more as the preform is not deviated in the injection pressure, which was inserted into a mold Kiyabiti one, the preform by vacuum suction Ya slide core such It is more preferable to fix to the mold cavity.
  • Adhesion Cut the worksheet and preform into strips with a width of 10 mm, and apply them between the layer (A), which is a colored calendar, and the layer (B), which is a modified olefin polymer, or heat of modification. After peeling off a part between the layer (D), which is a thermoplastic acryl-based polymer layer and / or the layer (B), which is a modified thermoplastic fluororesin, an instrument with an in-situ tester is used. T peeling was performed at a speed of 50 mm / min.
  • the transparent layer (T), the Z colored layer (A), the modified olefin polymer layer (B), and the backup layer (C) were laminated in this order.
  • the thickness of each layer of the obtained laminated sheet is as follows: transparent layer (T) 100 ⁇ colored layer ( ⁇ ) 200 / m, modified olefin polymer layer (B) 100 jum, and knock-up layer (C) 400 / zm. there were.
  • Transparent layer Polymethyl methacrylate (PMMA).
  • MN-modified polypyrene pyrene 100 g, MFRl. 0 g / 10 min.
  • HEMA-modified PE MN-modified PP used as the modified olefin polymer (B) in Example 1
  • MFR 1.0 gZl 0 min HEMA ⁇ O. 020 mol / Table 1 shows the results of the evaluation performed in the same manner as in Example 1 for H3 ⁇ 45 except that 100 g was used.
  • Example 1 In place of the white PMMA used as the felling fellow (A) in Example 1, 5 parts by weight of Daiwa Metal Powder Co., Ltd. aluminum paste, trade name "SAP771N" was added to 100 parts by weight of polymethyl methacrylate at 210 ° C. Table 1 shows the results of the evaluation performed in the same manner as in Example 1 of H 1S except that the colorless PMMA obtained by melting was used.
  • the thickness of each layer of the obtained laminated sheet is as follows: transparent layer (T) 100 / m. Colored layer (A) 200 ⁇ m, modified thermoplastic acrylic polymer layer (D) 100 rn, modified olefin polymer layer.
  • Transparent layer Polymethyl methacrylate (PMMA)
  • GMA-modified polymethyl methacrylate obtained by melting 20 parts by weight at 210 ° C.
  • Difficult case 6 Instead of the GMA-modified PMMA used as the modified thermoplastic acrylic polymer layer (D) in Example 5, 80SS part of polymethyl methacrylate and methyl methacrylate hydroxyethyl methacrylate copolymer (MMA-HEMA copolymer,
  • Table 1 shows the results of evaluation in the same manner as in Example 5, except that ⁇ modified PMMA obtained by melting 20 parts by weight at 210 ° C was used.
  • the transparent layer ( ⁇ ) / colored layer ( ⁇ ) -modified modified polymer layer ( ⁇ ) / backup layer (C) were laminated in this order.
  • the thickness of each layer of the obtained laminated sheet was 100 um for the transparent layer ( ⁇ ), 200 m for the colored layer (A), 100 m for the modified olefin polymer layer (B), and 400 um for the knock-up layer (C).
  • Transparent layer Polymethyl methacrylate (PMMA).
  • Wear feS Polymethyl methacrylate 80 parts by weight of methyl methacrylate Addition of 20 parts by weight of glycidyl acrylate copolymer (MMA-GMA copolymer, GMA ⁇ iO. 35 mol / "100 g") and 2 parts by weight of ICI titanium oxide, trade name "RTC 30" White GMA-modified polymethacrylate (white GMA-modified PMMA) obtained by melting at 210 ° C.
  • MMA-GMA copolymer GMA ⁇ iO. 35 mol / "100 g
  • RTC 30 White GMA-modified polymethacrylate
  • MN-modified polypropylene 100 g, MFRl. Og / 10 min.
  • Example 8 In place of white GMA modified ⁇ used as coloring agent ( ⁇ ) in Example 8 80 SS part of poly (methyl methacrylate) and a copolymer of methyl methacrylate-hydroxechinole methacrylate ( ⁇ - ⁇ copolymer ⁇ HEMA ⁇ gO. 30 mol Zl 00g) Evaluation results in the same manner as in Example 8 except that 20 SS part and IC I3 ⁇ 4h titanium oxide, 2 parts by weight of trade name “RTC30” were added and white HEMA-modified PMMA obtained by melting at 210 was used. Are shown in Table 1.
  • Example 11 Each of the following materials is melted using three m $ extruders, and each layer is sequentially extruded by a feed block, extruded from a T-die, and formed by a forming roll consisting of three polishing rolls. By cooling and shaping, a co-extruded multilayer laminated sheet having the following layer constitution was prepared. At that time, the temperature of the feed block and the T-die was set to 230 ° C. (Layer structure)
  • the colored layer (A) / modified olefin polymer was employed (B) and the Z-packed layer (C) was laminated in this order.
  • the thickness of each layer of the obtained laminated sheet was 200 ⁇ m / m for the feather (A) and 100 m for the modified olefin polymer layer (B) and 500 m for the backup layer (C).
  • Knockup layer (H: polypropylene (PP) with MFR of 0.5 gZl 0 min.) Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • each of the following materials is melted using three mt-type extruders, each layer is sequentially employed by a feed block, extruded from a T die, and cooled by a roll composed of three polishing rolls.
  • a co-extruded multilayer sheet having the following layer configuration was formed.
  • the feed block and T die were set at 230 ° C.
  • C Layer composition
  • Table 2 shows the results of the evaluation performed in the same manner as in Example 1 except that the following materials were used instead of the layered materials used in Example 1.
  • Transparent layer PVDF
  • PVDF polyvinylidene fluoride
  • HEMA-modified PE MN-modified PP used as the modified olefin polymer layer (B) in Example 13
  • HEMA-modified PE MFR 1.0 gZl 0 min, HEMA S.020 mol / 100 g
  • Table 2 shows the results obtained in the same manner as in Example 13 except for using.
  • Example 13 In place of the white PVDF used as the colored layer ( ⁇ ) in Example 13, 100 parts by weight of polyvinylidene fluoride was added with 5 parts by weight of Daiwa Metal Powder Industrial: tSi aluminum paste, trade name “SAP771N”. Table 2 shows the results of the evaluation performed in the same manner as in Example 13 except that the metallic PVDF obtained by melting at 210 ° C was used.
  • Table 2 shows the results obtained in the same manner as in Example 5 except that the composition of the co-extruded multilayer laminated sheet prepared in Example 5 and the materials constituting the layers were changed as follows. (Layer structure)
  • the transparent layer (T) / colored layer (A) modified thermoplastic fluororesin layer (D) / modified olefin polymer layer (B) and Z backup layer (C) were laminated in this order.
  • the thickness of each layer in the obtained laminated sheet is 100 m for the transparent layer (T), 20 O ⁇ m for the colored layer (A), 100 nm for the modified thermoplastic resin layer (D), 100 nm for the modified olefin polymer layer (B). ) 100 ⁇ , Knock-up layer (C) 300 m.
  • Transparent layer PVDF : polyvinylidene fluoride (PVDF :).
  • A White polyvinylidene fluoride obtained by adding 2 SS parts of titanium oxide manufactured by IC 1 company and “RTC 30” to 100 parts by weight of polyvinylidene fluoride and melting at 210 ° C.
  • RTC 30 Modified thermoplastic fluororesin layer
  • D Polyvinylidene fluoride 80S * part and methyl methacrylate-glycidyl methacrylate copolymer (MMA-GMA copolymer, GMA ⁇ SO. 35mol / 100g) 2) GMA-modified polyvinylidene fluoride (GMA-modified PVDF) obtained by melting 2 OfiJt part at 210 ° C
  • Example 17 instead of the GMA-modified PVDF used as the modified thermoplastic resin layer (D), 80 parts by weight of polyvinylidene fluoride and a copolymer of methyl methacrylate-hydroxyethyl methacrylate (including MMA-HEMA copolymer and HEMA) (0.30 mol / 100 g) 2 Obtained by fusing the OSS part at 210 ° C. Table 2 shows the results of the evaluation performed in the same manner as in Example 17 except that HEMA-modified PVDF was used.
  • MMA-HEMA copolymer and HEMA methyl methacrylate-hydroxyethyl methacrylate
  • Example 17 80 parts by weight of polyvinylidene fluoride and methyl methacrylate-methacrylic acid copolymer (MMA-MAA copolymer) were used instead of the GMA-modified PVDF used as the modified thermoplastic fluororesin layer (D) in Example 17.
  • Table 2 shows the results of iHffi in the same manner as in Example 17 except that MAA-modified PVDF obtained by melting the Offlt portion at 210 ° C was used.
  • Table 2 shows the results obtained in the same manner as in Example 8 except that the material of the layer configuration used in Example 8 was changed to the following material.
  • T Polyvinylidene fluoride
  • MMA-GMA copolymer Ofifi part and methyl methacrylate-glycidyl methacrylate copolymer (MMA-GMA copolymer, GMA S0.35 mol 1008) 20 parts by weight and ICI material: tS titanium oxide, White GMA-modified polyvinylidene fluoride (white GMA-modified PVDF) obtained by adding 2 parts by weight of trade name “RTC30” and melting at 210 ° C.
  • RTC30 trade name
  • Example 20 instead of the white GMA-modified PVDF used as colored layer (A) in Example 20 80 parts by weight of polyvinylidene fluoride and 20 parts by weight of methyl methacrylate monohydric methacrylate kissil copolymer (MMA-HEMA copolymer, HEMA content 0.30 mol / 100 g) and titanium oxide manufactured by ICI Table 2 shows the results of the evaluation performed in the same manner as in Example 20, except that 2 parts by weight of the trade name “RTC30” was added and the white HEMA-modified PVDF obtained by melting at 210 ° C. was used.
  • MMA-HEMA copolymer methyl methacrylate monohydric methacrylate kissil copolymer
  • RTC30 trade name
  • Table 2 shows the results of the evaluation performed in the same manner as in Example 11 except that the layered material used in HJfe Example 11 was changed to the following material.
  • Example 12 except that the material of the layer constitution used in Example 12 was changed to the following material Table 2 shows the results of the evaluation performed in the same manner as described above.
  • MMA-GMA copolymer methyl methacrylate-glycidyl methacrylate copolymer
  • GA S0.35 mol 1008 methyl methacrylate-glycidyl methacrylate copolymer
  • White GMA-modified polyvinylidene fluoride white GMA-modified PVDF obtained by adding 2 parts by weight of tin and trade name “RTC30” and melting at 210 ° C.
  • MN modified PP Maleic anhydride polypropylene 100 g, MFRl. 0 gZl 0 min.
  • Example 13 The results were evaluated in the same manner as in Example 13 except that in place of the MN-modified PP used as the modified olefin polymer layer (B) in Example 13, unmodified polyethylene (PE) with MFR of 1.0 gZl 0 min was used. See Table 2.
  • PVDF b White PVDF c: Metallic color PVDF d: GMA modified PVDF e: HEMA modified PVDF f: MAA modified PVDF g: White GMA modified PVDF h: White H EMA modified P VD F i: White MA A modified PVDF '': ⁇ 1 ⁇ denature? ? 1 ⁇ : 0 ⁇ 1 eight modified 1 3 £ 1: HEMA modified PE m: PE n: PP o: PP genuine
  • the following transparent layer material was applied to a 50 m thick polyester film with good surface gloss using a reverse roll coater, and three heating plates each having a length of about 12 cm were used.
  • a multi-zone impinging air drying oven consisting of zones at a rate of approximately 7.5 mZ, the gas contained in the transparent layer material is removed, and a uniform transparent phase with a thickness of approximately 20 m is formed on the polyester film. Formed. ' ⁇ Of the three heating zones were, respectively, zone 1: 125 ° C, zone 2: 165 ° C, and zone 3: 200 ° C.
  • the following coloring layer material is applied on the dried transparent layer using a reverse roll coater, and ⁇ PJ gas is removed by the same method as for the transparent layer to obtain a uniform coloring with a thickness of about 20 ⁇ m.
  • a layer was formed on the transparent layer.
  • a film having a multilayer structure composed of the transparent layer, the layer, and the adhesive layer was formed on the polyester film.
  • thermoplastic olefin-based elastomer sheet having a thickness of 500 m, which is a backing layer material described below, were laminated at a speed of 5 m / min.
  • the roll temperature at that time was about 177 ° C., and the linear pressure per cm was 54 kg.
  • the laminated structure of the / adhesive feiiZ adhesive layer was peeled off from the polyester film to obtain a multilayer laminated sheet having the following layer constitution.
  • UV absorber Tinuvin 900 0.35
  • PVDF Polyfutsudani vinylidene
  • the coloring layer material was cyclohexane, di-methyl, which was first heated to about 55 ° C with PMMA. After being gradually mixed and dissolved in a solvent of sobutyl ketone and butyrolactone, and then cooled, PVDF was added to this mixture to prepare a state in which the PVDF was strongly dispersed in the PMMA mixed solution. Further, a black color was added to the mixed solution as black ⁇ S to prepare a black colored layer material. The amount of the pigment contained in this mixed solution was about 4.5% on a heavy S basis. This mixed solution contained a solid resin component consisting of about 651% PVDF and about 35% by weight of PMMA. (Adhesive layer material)
  • the adhesive layer material used was a chlorinated polypropylene solution (trade name: Hard Len 17LJ, toluene solution containing 30% by weight of chlorinated polypropylene having a chlorination rate of 35% by weight as a solid) manufactured by Toyo Bfil Inc.
  • a chlorinated polypropylene solution (trade name: Hard Len 17LJ, toluene solution containing 30% by weight of chlorinated polypropylene having a chlorination rate of 35% by weight as a solid) manufactured by Toyo Bfil Inc.
  • the knock-up material is a 500 m thick thermoplastic elastomeric elastomer (Mitsubishi Kasho “Thermolan 2510 B”) with a flexural modulus of about 5,200 kgZcm 2 and an MFR of 1. OgZIO). Was used.
  • the thus obtained laminated sheet is cut into a size of 30 cm x 30 cm, and fixed to the thigh zone using a machine manufactured by Asano Laboratory: 3 ⁇ 4Shin3 ⁇ 4 ⁇ machine, and the surface is ⁇ Jg from both sides using a far-infrared ceramic heater. After heating to 150 to 200 ° C., vacuum forming was performed in accordance with the above-described vacuum forming method, and excess sheet portions were cut off to obtain a preform having a balanced three-dimensional shape.
  • the typical dimensions of the vacuum mold used were 15 cm long x 15 cm wide and 5 cm deep (average expansion ratio 3.2 times).
  • the above preform was set in the mold cavity of the injection machine, and in contact with the backing layer, 8.2% by weight of ethylene ⁇ fi, 10,000 kg / cm 2 of flexural modulus, and MFR of 33 g / 10 min propylene-ethylene block copolymer Ethylene-propylene copolymer rubber with a viscosity of ML 1 + 4 of 70, density of 0.86 g / cm 3 at 60ftt part, 100 ° C 30 weight:! Part and talc having an average particle size of 5.0 / im or less and a specific surface area of 3.5 m 2 / g or less are melted at 210 ° C and injected at a resin temperature of 210 ° C. As a result, an integrated molded article (plastic part for automobile exterior) having a laminated sheet on the outer surface was obtained. Table 3 shows the results of evaluation of this body.
  • Comparative Example 3 in place of the thermoplastic elastomeric elastomer sheet used as a backing material, polypropylene having a flexural modulus of 11,000 kg / cm 2 and an MFR of 0.5 gZl 0 minutes (Mitsubishi Chemical Corporation) Table 3 shows the results of Hffi in the same manner as in Comparative Example 3 except that a 500 / m-thick sheet coated with “Mitsubishi Boripro EC9 J”) was used.
  • the coating process of a coating material and the use of a casting sheet can be omitted. It is possible to adopt a simple process without using a car, and to have a three-dimensional shape, such as bumpers, side moldings, mudguards, wheel caps, spoilers, etc. Application to iiit is expected to be large.
  • the present invention can be expected to be applied not only to exterior members of automobiles but also to, for example, household articles and body parts.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne une plaque stratifiée multicouche coextrudée dont la caractéristique est de comporter, d'une part une couche colorée (A) en polymère acrylique thermoplastique et/ou en fluoro-résine, incluant dans les deux cas un colorant, d'autre part une couche (B) en polymère d'oléfine modifiée contenant au moins un groupe fonctionnel appartenant au groupe des carboxyl, anhydride d'acide, hydroxyl et glycidyl, et enfin une couche de compensation (C) en polymère d'oléfine. Ces trois couches (A, B, C) sont stratifiées les unes au-dessus des autres dans l'ordre (A)-(B)-(C). L'invention concerne également un procédé de confection d'objet moulé en plastique consistant d'abord à stratifier, d'une part une couche colorée (A) en polymère acrylique thermoplastique et/ou en fluoro-résine, incluant dans les deux cas un colorant, d'autre part une couche (B) en polymère d'oléfine modifiée contenant au moins un groupe fonctionnel appartenant au groupe des carboxyl, anhydride d'acide, hydroxyl et glycidyl, et enfin une couche de compensation (C) en polymère d'oléfine, ces trois couches (A, B, C) étant stratifiées les unes au-dessus des autres par coextrusion multicouche dans l'ordre (A), (B) et (C) de façon à obtenir une plaque. Le procédé consiste ensuite à thermoformer la plaque pour obtenir une avant-forme en relief, à introduire l'avant-forme dans un moule à injection, puis à mouler par injection un polymère d'oléfine de façon qu'il vienne en contact avec la couche de compensation.
PCT/JP1997/001908 1996-06-06 1997-06-05 Plaque stratifiee multicouche coextrudee et procede de confection d'objet moule en plastique utilisant une telle plaque WO1997046383A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP14418496 1996-06-06
JP8/144184 1996-06-06
JP8/148877 1996-06-11
JP14887796 1996-06-11

Publications (1)

Publication Number Publication Date
WO1997046383A1 true WO1997046383A1 (fr) 1997-12-11

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PCT/JP1997/001908 WO1997046383A1 (fr) 1996-06-06 1997-06-05 Plaque stratifiee multicouche coextrudee et procede de confection d'objet moule en plastique utilisant une telle plaque

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06182939A (ja) * 1992-12-17 1994-07-05 Dainippon Printing Co Ltd 外装用シート及び該外装用シートを利用した樹脂成形体
JPH06234183A (ja) * 1992-09-03 1994-08-23 Hitachi Kasei Polymer Kk 自動車内装部品の製造方法
JPH08108448A (ja) * 1994-10-06 1996-04-30 Kansai Paint Co Ltd プラスチック成型品の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06234183A (ja) * 1992-09-03 1994-08-23 Hitachi Kasei Polymer Kk 自動車内装部品の製造方法
JPH06182939A (ja) * 1992-12-17 1994-07-05 Dainippon Printing Co Ltd 外装用シート及び該外装用シートを利用した樹脂成形体
JPH08108448A (ja) * 1994-10-06 1996-04-30 Kansai Paint Co Ltd プラスチック成型品の製造方法

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