WO2000061368A1 - Corps composite renfermant une couche de mousse de resine polystyrenique et une couche de resine thermoplastique - Google Patents

Corps composite renfermant une couche de mousse de resine polystyrenique et une couche de resine thermoplastique Download PDF

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Publication number
WO2000061368A1
WO2000061368A1 PCT/JP1999/005996 JP9905996W WO0061368A1 WO 2000061368 A1 WO2000061368 A1 WO 2000061368A1 JP 9905996 W JP9905996 W JP 9905996W WO 0061368 A1 WO0061368 A1 WO 0061368A1
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WIPO (PCT)
Prior art keywords
resin
layer
composite material
thermoplastic resin
weight
Prior art date
Application number
PCT/JP1999/005996
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English (en)
Japanese (ja)
Inventor
Akira Iwamoto
Manabu Sato
Kenichi Takase
Toru Kino
Takasi Muroi
Yoshiaki Momose
Original Assignee
Jsp Corporation
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.)
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Priority claimed from JP10325899A external-priority patent/JP4059415B2/ja
Application filed by Jsp Corporation filed Critical Jsp Corporation
Priority to AU63671/99A priority Critical patent/AU6367199A/en
Publication of WO2000061368A1 publication Critical patent/WO2000061368A1/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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • B32B27/065—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 foam
    • 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
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0228—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • 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
    • B32B2325/00—Polymers of vinyl-aromatic compounds, e.g. polystyrene
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate

Definitions

  • the present invention relates to a composite material, and more particularly to a sheet or plate-like composite material having a polystyrene resin foam layer and a thermoplastic resin layer.
  • Expanded polystyrene sheets are widely used as materials for thermoforming various containers such as trays, bowls, and cups.
  • foamed polystyrene sheets have poor oil and solvent resistance.
  • its heat resistance is relatively low, and when the container is heated in a microwave oven, it tends to be deformed.
  • Japanese Utility Model Publication No. 62-209-69 discloses that foamed polystyrene is used as an adhesive with a mixture of polybutadiene, polyisoprene, styrene-butadiene copolymer, or a mixture of thermoplastic rubber and polyethylene.
  • a composite sheet is shown in which a polyolefin resin film is adhered to a sheet.
  • thermoplastic rubber which is more than three times more expensive than polystyrene, polyethylene, etc.
  • the adhesive strength cannot be sufficiently satisfied.
  • 62-137384 proposes that urethane or an ethylene / vinyl acetate copolymer is used as an adhesive, but it is effective to use a used laminate effectively. It has problems that it cannot be recycled, the laminate has low heat resistance, and the ethylene // vinyl acetate copolymer has a strong odor.
  • the method of recycling this multilayer film is to separate it into layers, to recover each resin, to melt the multilayer film, and then to recover each resin by fractional distillation, and to multilayer film. There is a method of melting and recovering as a resin mixture. The former two methods are not advantageous in terms of cost.
  • the third method requires that the mixture be free of substances that would interfere with the purpose of reuse.
  • the present invention has been made in view of the above-mentioned problems of the prior art, and is a composite material including a polystyrene resin foam layer and a thermoplastic resin layer, wherein the adhesive strength of both layers is a composite material such as a bowl. It is an object of the present invention to provide a composite material that is high enough to withstand the formation of a deep container, has high oil resistance, is inexpensive, and can be recycled.
  • a polystyrene resin foam layer an alloy layer provided on at least one of both surfaces of the polystyrene resin foam layer, and a thermoplastic resin layer provided on the aperture layer.
  • the thermoplastic resin layer is selected from a polyolefin resin and a polyester resin. Made of plastic
  • the alloy layer is composed of a mixture of a polystyrene resin and a thermoplastic resin selected from a polyolefin resin and a polyester resin.
  • a thermoplastic resin layer is composed of a polyolefin resin
  • the resin heat of the alloy layer is reduced.
  • the plastic resin is a polyolefin resin
  • the thermoplastic resin layer is made of a polyester resin
  • the resin thermoplastic resin of the alloy layer is a polyester resin
  • a composite material having an adhesive strength between the polystyrene resin foam layer and the thermoplastic resin layer of 98 OmN / 25 mm or more is provided.
  • FIG. 1 is a diagram showing a graph of crystallization time measurement.
  • the polystyrene resin used for the polystyrene resin foam layer in the present invention includes a homopolymer and a copolymer of styrene.
  • the styrene monomer unit contained in the copolymer is at least 25% by weight or more, preferably 50% by weight or more.
  • polystyrene resin examples include polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, and styrene-acrylic acid copolymer.
  • Polymer styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl acrylate
  • examples thereof include a copolymer, a styrene-maleic anhydride copolymer, a polystyrene-polyphenylene ether copolymer, and a mixture of polystyrene and polyphenylene ether.
  • Polypropylene resin or its hydrogenated product is blended.
  • Polyolefin resin such as polypropylene resin or high-density polyethylene is blended at a ratio of 20% by weight or less in consideration of mixing of recycled resin. be able to.
  • the heat resistance of the composite material of the present invention can be improved by using a polystyrene resin having a vicat softening point of 110 ° C. or higher.
  • the vicat softening point of the resin refers to a value determined by JIS K7206 (test load is ⁇ method, heating rate of heat transfer medium is 50 ° CZ).
  • the melt viscosity of polystyrene resin is the melt viscosity under the conditions of 190 ° C and a shear rate of 100 sec- 1 . It is more than 20 Pa and less than 10 Pa, less than OOOPa. 0 0-5, OOOP a 's. If the melt viscosity is less than 20 Pa ⁇ s, the molten resin extruded from the die at the time of foam molding may sag, making molding difficult. On the other hand, if it exceeds 10, OOOP a 's, the extrusion pressure will increase and extrusion molding will be difficult, and there is a possibility that high quality foams cannot be molded.
  • Polystyrene density of the resin foam layer is usually 0. 0 3 5 ⁇ 0. 7 g Z cm 3, preferably 0. 0 5 ⁇ 0. 5 g Z cm 3, particularly those for thermoforming 0. 0 7 ⁇ 0. 5 g / cm 3 things Shi preferred Rere.
  • density is less than 0. 0 3 5 g / cm 3 , or insufficient strength of the molded article obtained by molding a composite material, a hole in the molded article results in lack of elongation when heated vacuum forming May occur.
  • its density is greater than 0.7 g Z cm 3, it is economically disadvantageous.
  • the heat insulation of the molded article such as a container is deteriorated. For example, when hot water is poured, the container cannot be held by hand.
  • the thickness of the polystyrene resin foam layer is usually 0.5 to 10 mm, preferably 0.7 to 5 mm, especially 0.7 to 4 mm for thermoforming. Is preferred. If the thickness of the foam layer is less than 0.5 mm, the wall thickness of the molded product obtained by vacuum forming or the like becomes insufficient, and the strength and the heat insulating property tend to be inferior. On the other hand, if the thickness is more than 10 mm, uneven heating inside and outside of the sheet is likely to occur during heating vacuum forming, and precise temperature control is required.
  • the open cell ratio (A STM D 285, Procedure C) of the foam layer is preferably 40% or less.
  • the open cell ratio of the foam layer affects the secondary foaming property at the time of thermoforming and the quality (physical properties such as strength) of the obtained secondary molded product.
  • the polystyrene resin foam layer can be obtained by any known method using a foaming agent such as an organic foaming agent, an inorganic foaming agent, or a decomposable foaming agent.
  • a foaming agent such as an organic foaming agent, an inorganic foaming agent, or a decomposable foaming agent.
  • the organic blowing agent include propane, n-butane, i-butane, a mixture of n-butane and i-butane, aliphatic hydrocarbons such as pentane and hexane, and cyclic compounds such as cyclobutane and cyclopentane.
  • Aliphatic hydrocarbons trichlorofluoromethane, dichlorodifluoromethane, 1, 1—difluoroethane, 1,1—diphneololol 1—chloroethane, 1,1,1,2, -tetranoleoloethane, methyl chloride, ethyl chloride And halogenated hydrocarbons such as methylene chloride, and mixtures thereof.
  • the inorganic foaming agent include a gas such as nitrogen and carbon dioxide and water.
  • examples of the decomposable blowing agent include azodicarbonamide, dinitrosopentamethylentramine, azobisisobutyronitrile, sodium bicarbonate and the like.
  • foaming agents can be appropriately mixed and used. Among them, it is preferable to use a material that does not contain hydrogen hydride and has little effect on the environment such as destruction of the ozone layer.
  • the amount of the foaming agent used is not particularly limited, but is generally in the range of 0.01 to 0.1 mol per 100 g of the resin.
  • various additives which are usually added to the polystyrene resin as needed, for example, a nucleating agent, an antioxidant, a heat stabilizer, so long as the object of the present invention is not significantly impaired.
  • An antistatic agent, a conductivity-imparting agent, a weathering agent, an ultraviolet absorber, a coloring agent, a flame retardant, an inorganic filler and the like can be added.
  • the thermoplastic resin used for the thermoplastic resin layer laminated on the polystyrene resin foam layer includes a polyolefin resin or a polyester resin.
  • the thickness of the thermoplastic resin layer is generally 0.1 to 1 mm, preferably 0.15 to 0.8 mm, more preferably 0.015 to 0.35 mm, and the polystyrene
  • the ratio to the thickness of the resin foam layer is generally 3 to 50%, preferably 5 to 40%. If the thickness of the thermoplastic resin layer is smaller than the above-mentioned range, the sheet is likely to have through holes and breakage during secondary molding, which is not preferable. On the other hand, if the thickness is too large, the foaming layer may be melted if the composite material is molded with the best heating time for the thermoplastic resin layer as well as the cost.
  • thermoplastic resin layer it is preferable to use a high-density polyethylene-polypropylene resin as the thermoplastic resin layer in terms of heat resistance and appearance.
  • high-density polyethylene is used, the surface of the composite material has a matte appearance.
  • polypropylene resin is used, a composite material having excellent surface gloss can be obtained.
  • polyester resin for the thermoplastic resin layer from the viewpoints of fragrance retention and gas barrier properties.
  • thermoplastic resin layer various additives such as antioxidants, heat stabilizers, antistatic agents, conductivity-imparting agents, nucleating agents, weathering agents, UV inhibitors, etc.
  • thermoplastic resin layer Add 1 to 100 nm of kaolin, myriki, silica, tanolek, creis, zinc methacrylate, highly saturated nitrile rubber, liquid crystal polymer, etc. in an amount of 3 to 10% by weight based on the resin. It can be finely dispersed to form a so-called nanocomposite. As a result, the tensile strength, tensile modulus, bending strength, bending modulus, gas permeability, transparency, flame retardancy, heat stability, and the like are improved. If necessary, a compatibilizer can be added for dispersion.
  • thermoplastic resin layer laminated on the polystyrene resin foam layer in addition to the thermoplastic resin layer laminated on the polystyrene resin foam layer, a film-like polyamide resin, vinylidene chloride, saponified ethylene vinyl acetate copolymer, and It can also be laminated with the foam as a composite material by combining with other functional materials such as lumidium foil.
  • thermoplastic resin layer formed of polyolefin resin or polyester resin should be provided as the outermost layer of the composite material. Can be.
  • thermoplastic resin layer Next, the polyolefin resin and the polyester resin forming the thermoplastic resin layer will be described in detail.
  • the polyolefin resin includes homopolymers, copolymers (random copolymers, block copolymers, and the like) of olefins, and blends.
  • copolymers random copolymers, block copolymers, and the like
  • the upper limit of the softening point is particularly limited
  • it is about 160 ° C.
  • it is particularly preferable to use high-density polyethylene or polypropylene resin.
  • the propylene resin includes homopolymers, copolymers and blends of propylene.
  • the copolymer component includes ethylene, butylene and other monoolefins, and the ⁇ -olefin has 12 or less, preferably 8 or less carbon atoms.
  • the content of the copolymer components, ethylene, butylene and other monoolefins, is 20% by weight or less for block copolymers and 8% by weight or less for random copolymers. Preferably.
  • the resin for the blend includes a homopolymer of ethylene, a copolymer of ethylene and an ⁇ -olefin having 3 to 12 carbon atoms, and a carbon number of And the homopolymers of "one-olefin" having 4 to 6 are exemplified.
  • the polyolefin resin for forming the thermoplastic resin layer has (i) a melting point of 150.
  • a mixture of a polypropylene resin having a melting point of not more than C (hereinafter, also referred to as a low melting point polypropylene resin) and a polyethylene resin having a melting point of not less than 130 ° C (hereinafter, also referred to as a high melting point polyethylene resin);
  • a polypropylene resin exceeding C hereinafter also referred to as a high-melting-point polypropylene resin
  • a resin having a melting point of 130 and a main component of the above-mentioned polyethylene resin are used.
  • the “main component” means that the resin or mixed resin (i) to (iii) is about 80% by weight of the thermoplastic resin layer. /. Within the range not impairing the object and effect of the present invention, for example, 70 parts by weight or less of a polystyrene resin of 100 parts by weight or less of the resin (i) to (iii) or a mixed resin, It means that other polymers such as nylon resin, polyester resin, rubber and the like may be further included.
  • the low-melting polypropylene resin includes a copolymer of propylene and the like.
  • the copolymer component includes ethylene, butylene, and other ⁇ -olefins, and the ct-olefin has a carbon number of 12 or less, preferably 8 or less.
  • the content of the copolymer components, ethylene, butylene, and other ⁇ -olefins, is 8% in the case of a random copolymer. / 0 or less is preferable.
  • the melting point of the low melting point polypropylene resin is preferably at least 138 ° C.
  • a particularly preferred melting point range of the low melting point polypropylene resin is 140 to 150 ° C.
  • the high melting point polypropylene resin includes propylene homopolymers and copolymers.
  • As the high melting point polypropylene resin various conventionally known ones can be used.
  • the upper limit of the melting point is usually about 165 ° C. Its preferred melting point range is 158 to 164 ° C.
  • the high-melting-point polyethylene resin includes a copolymer of ethylene and ⁇ -olefin having 3 to 12 carbon atoms, and examples thereof include conventionally known various materials such as high-density polyethylene.
  • the upper limit of the melting point is usually 140 ° C. Its preferred melting point range is 132-138 ° C.
  • the amount of the low melting point polypropylene resin is preferably less than 100% by weight, more preferably 70% by weight, based on the total weight of the low melting point polypropylene resin and the high melting point polyethylene resin.
  • the amount of the high melting point polyethylene resin is preferably 0% by weight. / 0 more than 85 weight. /.
  • the content is more preferably 30 to 70% by weight.
  • the polyolefin resin constituting the thermoplastic resin layer has the above-mentioned composition (i) to (iiii) and has a high crystallization rate.
  • the semi-crystallization time of the polyolefin resin at 100 ° C. is 30 seconds or less, preferably 2 to 28 seconds. If the time exceeds 30 seconds, the moldability will deteriorate.
  • the half-crystallization time referred to in this specification was previously set at 300 ° C using a crystallization rate measuring device (MK-801 type manufactured by Meto Co., Ltd. (former Kotaki Shoji Co., Ltd.))
  • the heated resin sample can be put into a crystallization bath set at 100 ° C. for measurement.
  • the measurement sample should be in the form of a film.
  • the thickness of the finolem shall be 0.1 ⁇ 0.2 mm, and the dimensions of the film shall be 15 x 15 mm square. This is sandwiched between power microscope glasses and used as a measurement sample.
  • the support value is 3 V.
  • the crystallization rate measuring device manufactured by Metron Co., Ltd. is a device for determining the degree of crystallinity from the relationship between the crystallization of a sample and the birefringence of light, and the half-crystallization time referred to in this specification is defined as It is determined from the obtained time-birefringence light quantity curve (I) shown in FIG. That is, the amount of light due to birefringence in the sample increases with time, and finally becomes constant (value ⁇ ) after time point a.
  • the half-crystallization time is the time c in the curve (I) that gives the amount of light B equal to ⁇ 2.
  • (II) represents a change in the bath temperature when the crystallization bath temperature is set to a temperature D (100 ° C. in the case of the present invention).
  • thermoplastic resin layer a polyester resin can be used in addition to the polyolefin resin described above.
  • Polyester resin is dicarboxylic acid II
  • Method of polycondensing component and diol component It is produced by transesterification of polyester homopolymer and Z or polyester copolymer.
  • the polyester resin an aromatic polyester resin having a half-crystallization time at 100 ° C. of 30 minutes or more is preferably used.
  • the aromatic polyester resin is composed of a dicarboxylic acid component and a diol component, at least one of which is aromatic.
  • dicarboxylic acid component of the aromatic polyester resin dicarboxylic acid or an ester-forming derivative thereof can be used.
  • the ester-forming derivatives include ester derivatives such as dimethyl ester and getyl ester, salts such as diammonium salts, and acid halides such as dichloride.
  • the dicarboxylic acid component units in the polymer include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, phthalic acid, 4,4'-diphenyl carboxylic acid, and 3,4'-diphenyl Aromatic dicarboxylic acids such as dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and esters thereof
  • a component unit derived from a forming derivative or a component unit derived from an aliphatic dicarboxylic acid such as oxalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid or an ester-forming derivative thereof; or Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, 1,3-cyclohexane
  • diol component of the aromatic polyester resin used in the present invention aliphatic and aromatic diols (including divalent phenol) can be used.
  • diol component unit in the polymer there are aliphatic diols such as ethylene glycol, cyclohexanedimethanol, propylene glycol, trimethylene daryl, diethylene glycol, and 1,4-butanediol, or esters thereof.
  • Alicyclic diols such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,6-cyclohexanediol, etc., or their ester formation
  • a component unit derived from an aromatic diol such as bisfuninol A or an ester-forming derivative thereof.
  • the above aromatic polyester resin may have its molecular end sealed with a component unit derived from a monofunctional compound such as a small amount of benzoic acid, benzoyl benzoic acid, methoxypolyethylene glycol, or the like. Les ,. Also, it may contain a small amount of a component unit derived from a polyfunctional compound such as pyromellitic acid, trimellitic acid, trimesic acid, glycerin, and pentaerythritol.
  • a monofunctional compound such as a small amount of benzoic acid, benzoyl benzoic acid, methoxypolyethylene glycol, or the like. Les ,.
  • a component unit derived from a polyfunctional compound such as pyromellitic acid, trimellitic acid, trimesic acid, glycerin, and pentaerythritol.
  • the half-crystallization time of the aromatic polyester resin can be adjusted by using two or more dicarboxylic acid components such as terephthalic acid and isophthalic acid to change the molar ratio of the dicarboxylic acid component units. It can be adjusted by using two or more kinds of diol components such as ethylene glycol and cyclohexanedimethanol and changing the molar ratio of the diol component units.
  • an aromatic polyester copolymer having a half-crystallization time of 30 minutes or more is preferable. Particularly preferred examples are 75 to 40 mol. / 0 ethylenic glycol and 25-60 mol 0 /. Diol component consisting of cyclohexanedimethanol And a dicarboxylic acid component composed of terephthalic acid.
  • the film-like aromatic polyester resin may be a polyolefin resin such as a polystyrene resin, a polypropylene resin, or a polyethylene resin, a nylon resin, or a high-molecular-weight resin as long as the object of the present invention is not impaired.
  • Resins such as impact polystyrene, styrene-containing thermoplastic elastomers, etc., elastomers and rubbers are approximately 40% by weight. /. It may be contained in the following proportions.
  • the thickness of the polyester resin is preferably from 0.01 to 0.5 mm, particularly preferably from 0.03 to 0.2 mm. If it is less than 0.01 mm, it is stretched and further thinned during thermoforming, so that breakage and pinholes are liable to occur, and the solvent resistance of the composite material is liable to decrease, and it is difficult to obtain sufficient oil resistance. If it exceeds 0.5 mm, it will be difficult to adhere to the polystyrene resin foam, resulting in high cost. Also, from the viewpoint of the recyclability of the composite material, the amount of the laminated polyester resin is 50% by weight of the composite material. /. Hereinafter, the content is preferably 25% by weight or less.
  • the adhesive strength between the polystyrene resin foam layer and the thermoplastic resin layer of the composite material of the present invention is 980 mNZ25 mm or more, particularly preferably 2451 mN / 25 mm or more, and more preferably 3677 mN. It has a large value of 25 mm or more. ⁇ The upper limit of the adhesive strength is usually about 122 58 mN / 25 mm. A composite material having such a large interlayer adhesive strength is provided for the first time by the present invention.
  • the interlayer adhesive strength of the composite material of the present invention having a large value as described above means that the phase structure index PI value between the polystyrene resin foam layer and the thermoplastic resin layer is 0.5 to: 1.5, Preferably 0.6 to: 1.4, more preferably 0.6. This is due to having an alloy layer in the range of 7 to 1.3. The following is a description of the error layer.
  • the alloy layer is mainly composed of a mixed resin of a polystyrene resin and a thermoplastic resin, and the weight ratio of the polystyrene resin to the thermoplastic resin is 95: 5 to 30:70, and 90:10 to 40:40. : 60, particularly preferably 85: 15 to 55: 45.
  • the total amount of the polystyrene resin and the thermoplastic resin is 50% by weight or more based on the alloy layer.
  • the thermoplastic resin used for the alloy layer the same resin as the thermoplastic resin used for the thermoplastic resin layer laminated on the alloy layer, or the same kind of thermoplastic resin that can be heat-fused is used. Is preferably used.
  • the amount of polystyrene resin in the mixed resin of the alloy layer exceeds 95: 5
  • the adhesive strength between the alloy layer and the polystyrene foam layer can be satisfied, but the adhesive strength between the alloy layer and the thermoplastic resin layer can be improved. May be insufficient in adhesive strength.
  • the amount of the polystyrene resin is lower than 30:70, the adhesive strength between the alloy layer and the thermoplastic resin layer can be satisfied, but the adhesive strength between the polystyrene resin foam layer and the alloy layer can be improved. The strength may be insufficient.
  • the thickness of the alloy layer is in the range of 15 to 200 m, and the adhesive strength tends to increase as the thickness increases, and is preferably 20 to 150 / j m.
  • the thickness of the alloy layer is 3 to 50%, preferably 5 to 40% of the thickness of the polystyrene resin foam layer. If the thickness of the alloy layer is less than 3%, the adhesion becomes insufficient, while if it exceeds 50%, the foam layer is heated when the alloy layer is laminated on the foam layer, and as a result, the foam The open cell ratio of the layer tends to be high, and also causes cost increase.
  • polyester resin is used as the thermoplastic resin of the alloy layer, the melting point ig
  • the melting point in the present specification is determined from a melting peak of a DSC curve obtained by a heat flux differential scanning calorimetry performed in accordance with JIS K7112. Details are as follows. Approximately 5 mg of a film having a thickness of 0.5 mm or less is used as a test piece. Immediately after the temperature is raised to 0 ° C higher, the temperature is lowered to 40 ° C in a cooling rate of 10 ° CZ, and then immediately at a heating rate of 10 ° C / min. The melting point is defined as the peak temperature of the melting peak of the DSC curve (when two or more melting peaks are present, the melting peak area is larger) when the temperature is raised to about 30 ° C higher.
  • additives such as a compatibilizer, an adhesive, an elastic component, a viscosity modifier and the like can be added to the alloy layer in an amount of less than 50% by weight based on the alloy layer.
  • the alloy layer preferably contains a compatibilizer.
  • a compatibilizer any one can be used as long as it can compatibilize the polystyrene resin and the thermoplastic resin of the alloy layer, and various conventionally known ones can be used.
  • the use of a styrene-containing thermoplastic elastomer not only improves the adhesion between the polystyrene foam layer and the thermoplastic resin layer, but also improves the impact strength and brittleness of the composite material. Is preferred.
  • the thermoplastic resin of the alloy layer is a polyester resin
  • the styrene-containing thermoplastic elastomer is made of polystyrene. It functions as a viscosity regulator for lowering the viscosity of the mixed resin of the polyester resin and the polyester resin, thereby improving the kneading property of the polystyrene resin and the polyester resin.
  • styrene-containing thermoplastic elastomer examples include styrene-ethylene-butylene-styrene-block copolymer (SEBS), styrene-ethylene-propylene-styrene-block copolymer (SEPS), and styrene-butadiene.
  • SEBS styrene-ethylene-butylene-styrene-block copolymer
  • SEPS styrene-ethylene-propylene-styrene-block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SBS or SIS has a polystyrene crystal phase as a hard segment, and has a structure in which polybutadiene or polyisoprene is block copolymerized as a soft segment.
  • SEBS and SEPS are obtained by highly hydrogenating polybutadiene and polyisoprene contained in SBS and SIS to saturate the double bonds in the main chain.
  • These styrene-containing thermoplastic elastomers such as SEBS, SEPS, SBS, and SIS are described in detail in “Plastic Age”, pp. 101-106. (June 1985) Have been.
  • the addition of the compatibilizer increases the adhesive strength between the polystyrene resin foam layer and the thermoplastic resin layer, and further increases the impact strength and brittleness of the composite material when the compatibilizer of the styrene-containing thermoplastic elastomer is used. Is improved.
  • the compatibilizer is generally added in an amount of from 0: to 30 parts by weight, preferably from 0.5 to 10 parts by weight, per 100 parts by weight of the total amount of the polystyrene resin and the thermoplastic resin in the alloy layer. You. In the case of a styrene-containing thermoplastic elastomer, the content is preferably 2 to 10 parts by weight.
  • This compatibilizer increases the adhesive strength between the polystyrene resin foam layer and the thermoplastic resin layer, Impact strength and brittleness are improved.
  • the styrene-containing thermoplastic elastomer is preferably used in an amount of 0.3 to 100 parts by weight of the total amount of the polystyrene resin and the polyester resin in the alloy layer. 20 parts by weight, more preferably 0.5 to 15 parts by weight, is added.
  • the styrene-containing thermoplastic elastomer acts as a compatibilizer, an elasticity-imparting agent, and a viscosity modifier, and is preferably added to the alloy layer.
  • An elastic component can be added to the alloy layer for the purpose of improving brittleness.
  • the elastic component a random copolymer, a block copolymer, a graft copolymer, or a mixture of these copolymers composed of a styrene component such as styrene or ⁇ -methylstyrene and a butadiene or isoprene-based gen component is used.
  • the elastic component is preferably added in an amount of 2 to 50 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight of the total of the polystyrene resin and the thermoplastic resin in the alloy layer. Parts by weight.
  • the elastic component containing the above-mentioned styrene-containing thermoplastic elastomer is used in the polystyrene resin foam layer in order to improve its brittleness, and is used in an amount of 0.5 to 30 parts by weight per 100 parts by weight of the polystyrene resin. Parts, preferably 1 to 20 parts by weight, can be added.
  • An adhesive such as an ethylene-vinyl acetate copolymer can be added to the alloy layer.
  • the ethylene / butyl acetate copolymer is preferably used in an amount of not more than 25 parts by weight per 100 parts by weight of the mixed resin of the polystyrene resin and the thermoplastic resin, from the viewpoint of economy and reduction of odor.
  • the alloy layer has a phase structure index ⁇ I value in the range of 0.5 to 1.5.
  • the phase structure index ⁇ ⁇ value indicates the mixed state of the polystyrene resin and the thermoplastic resin of the alloy layer, and is defined by the following equation (1).
  • PI value (7; ⁇ ⁇ ⁇ l3 ⁇ 4ZB ⁇ A) Equation (1) In the above equation (1), ⁇ .
  • melt viscosity of polystyrene resin at shear rate 100 sec ⁇ ' melt viscosity of polystyrene resin at shear rate 100 sec ⁇ '
  • ⁇ ⁇ volume fraction of thermoplastic resin phase in alloy layer
  • heat at 77 ⁇ 190 ° C shear rate 100 sec 1 It is the melt viscosity of the plastic resin.
  • the thermoplastic resin in the alloy layer is covered with the polystyrene resin and is hardly exposed on the bonding surface, and the bonding strength between the foam layer and the alloy layer is satisfactory.
  • the adhesive strength between the alloy layer and the thermoplastic resin layer is insufficient, and delamination occurs when the composite material is molded into a molded article such as a bowl or the like obtained by thermoforming.
  • the PI value comes to more than 1.5, polystyrene down resin Aroi layer is not easily exposed to the covered adhesive surface to the thermoplastic resin, the adhesion between the thermoplastic resins layer and Aroi layer Although the strength is satisfactory, the adhesive strength between the alloy layer and the foam layer is insufficient, and delamination tends to occur when the composite material is formed into a molded article such as a container.
  • the PI value is preferably in the range of 0.6 to 1.4, particularly 0.7 to 1.3, because of the excellent adhesive strength between the foam layer and the thermoplastic resin layer.
  • the composite material of the present invention can be manufactured by a conventionally known method.
  • a typical method an alloy layer and a thermoplastic resin layer are sequentially supplied to a previously produced foam layer by an extruder and adhered thereto; the previously produced foam layer and the thermoplastic resin layer are bonded together.
  • the composite material (multi-layer sheet) obtained by the multi-layer co-extrusion method has a thimble process and can be reduced in cost compared to other methods. It is preferable because the adhesion strength between the body layer and the alloy layer and between the alloy layer and the thermoplastic resin layer is increased.
  • the polystyrene resin, the thermoplastic resin, the compatibilizer, and the like used in the alloy layer may be dry-blended in a pellet form and then directly introduced into the inlet of an extruder, or may be melt-kneaded in advance.
  • the composite of the present invention has a structure in which a thermoplastic resin layer is provided on at least one surface via an alloy layer.
  • the other surface can be a polystyrene resin layer alloy layer. Since the polystyrene resin layer is excellent in printability and glossiness, it can be appropriately printed.
  • the alloy layer is also excellent in printability and glossiness, so that printing can be performed appropriately. Further, since two alloy layers can be simultaneously laminated on both sides of the foam layer by the co-extrusion method using the same extruder, the productivity is excellent.
  • HIPS high impact polystyrene
  • various additives which are usually added to the polystyrene resin and the thermoplastic resin as necessary, for example, a nucleating agent, an antioxidant, and a heat-stable agent, within a range not significantly impairing the object of the present invention.
  • Agents, antistatic agents, conductivity-imparting agents, weathering agents, ultraviolet absorbers, coloring agents, flame retardants, inorganic fillers, etc. go to various additives which are usually added to the polystyrene resin and the thermoplastic resin as necessary, for example, a nucleating agent, an antioxidant, and a heat-stable agent, within a range not significantly impairing the object of the present invention.
  • Agents, antistatic agents, conductivity-imparting agents, weathering agents, ultraviolet absorbers, coloring agents, flame retardants, inorganic fillers, etc. go
  • the composite material of the present invention is formed by laminating a polystyrene resin foam layer and a thermoplastic resin layer with extremely high adhesive strength, and is excellent in oil resistance and thermoformability. Since no special adhesive is used, it can be manufactured at low cost and is suitable for recycling. That is, the melted composite material can be reused as an alloy layer of the composite material.
  • thermoplastic resin layer by forming the thermoplastic resin layer with a polypropylene resin having a vicat softening point of 112 ° C. or higher, a composite material having excellent heat resistance can be obtained.
  • thermoplastic resin layer By forming the thermoplastic resin layer with a polyester resin having a half-crystallization time of 30 minutes or more, a composite material having excellent recyclability, thermoformability, and heat sealability can be obtained.
  • the polyester resin layer is excellent in oil resistance, fragrance retention, gas barrier properties, and adhesion to other wrap films, this composite material is particularly effective as a material for molding containers and the like.
  • Sheet composites having the configurations shown in Tables 1, 2, 5, and 6 were produced. Tables 1, 2, 5, and 6 also show the density (gZ cm 3 ) of this composite, the thickness of the composite ( mm ), and the type of composite material used in its manufacture. Indicated. Furthermore, Table 1, Table 2, Table 5 and Table 6, oil resistance of the composite material, the adhesive strength (mNZ25 mm) and continuous cell ratio of the foam layer of polyolefin resin layer (2 'or sigma 2) (% ) showed that.
  • Poriorefui down resin (Z 1) represents the surface layer
  • Poriorefui emission resin layer (Z 2) shows the back surface layer.
  • Z indicates the adhesive strength between the polyolefin resin layer (Z 1 ) forming the surface layer and the foam layer (X)
  • Z 2 ZX Indicates the adhesive strength between the polyolefin resin layer (Z) forming the backside layer and the foam layer (X).
  • the specific contents of the types of composite materials shown in Tables 1, 2, 5, and 6 are as follows.
  • the resin temperature shown in Table 1, Table 2, Table 5 and Table 6 is the resin temperature when extruded from the die (die) of the extruder.
  • the extruded cylindrical resin was cut open along the cooled cylinder having a diameter of 200 mm in the drawing and extrusion direction to obtain a polystyrene resin foam sheet, and the foam sheet was wound up.
  • a polyolefin resin film having a thickness shown in Table 1 or Table 2 was laminated on the obtained foamed sheet via an alloy layer shown in Table 3 or Table 4 to obtain a composite material.
  • the alloy layer was extruded with a 5 Omm diameter extruder from the raw material inlet through a prescribed amount of resin shown in Table 3 or Table 4 and, if necessary, an amount of phase shown in Table 3 or Table 4 per 100 parts by weight of alloy.
  • the solubilizer was heated and kneaded, and was extruded and supplied from a T-die having a width of 600 mm at 200 ° C.
  • extruders with a diameter of 65 mm and a diameter of 9 Omm as extruders for foam layers
  • An extruder with a diameter of 50 mm was used as the extruder for the polyolefin resin layer, and an extruder with a diameter of 40 mm was used as the extruder for the alloy layer.
  • the one with a cylindrical slit with a diameter of 84 mm and a thickness of 0.5 mm was used.
  • the foam layer was heated and kneaded with a prescribed amount of resin and additives from the raw material inlet using a 65 mm diameter extruder in the amounts shown in Table 3, Table 4, Table 7, or Table 8 per 100 parts by weight of resin. Then, the blowing agent and the amount shown in Table 3, Table 4, Table 7 or Table 8 are injected into the resin mixture adjusted to about 200 ° C., and then fed to an extruder having a diameter of 9 O mm. The resin temperature was adjusted as shown in Table 1, Table 2, Table 5, and Table 6.
  • the polyolefin resin layer is supplied from an extruder with a diameter of 50 mm
  • the alloy layer is supplied from an extruder with a diameter of 40 mm to one or both sides of the melt for forming a polystyrene resin foam layer, as required.
  • the melt was mixed with the melt for forming a foam layer inside the die and coextruded.
  • the alloy layer was added with a compatibilizer in an amount shown in Table 3, Table 4, Table 7, or Table 8 per 100 parts by weight of the alloy of the polystyrene resin and the polyolefin resin as required.
  • the composite material was wound up by pulling the extruded cylindrical resin along a cooled cylinder having a diameter of 200 mm.
  • Table 3 Table 4, the foam layer of the composite material shown in Table 7 or Table 8 (X), Aroi layer ( ⁇ ', ⁇ 2) and Poriorefui emission resin layer ( ⁇ ', ⁇ 2) the specific contents of It will be shown.
  • the amount (weight / 0 ) of the PS resin or the glass resin in the alloy layer is a value based on the total weight of 100% by weight of the PS resin and the glass resin.
  • 25 parts by weight of a resin (to be described later) was added as an elastic component to 100 parts by weight of the mixed resin of the PS resin and the ⁇ resin. did.
  • the resin ⁇ ⁇ described later as an elastic component in the alloy layer was added to 100 parts by weight of the mixed resin of the PS resin and the ⁇ resin. And 25 parts by weight.
  • the specific contents of the PS resin (polystyrene resin) indicated by reference numerals for the foam layer (X) are as described below.
  • the talc blended with the PS resin is Highfila # 12 manufactured by Matsumura Sangyo Co., Ltd.
  • B represents a butane mixture composed of 70 wt% of n-butane and 30 wt% of iso-butane
  • n-p represents n-pentane
  • CF 40 S represents "Hydrocerol CF 40 S" (chemical blowing agent) manufactured by Dainichi Seika Co., Ltd. is shown.
  • alloy layer ( ⁇ 2 ) The specific contents of the resin (polyolefin resin) and the compatibilizer are as described below.
  • the alloy composition of the alloy layer ( ⁇ 1 ) and the alloy layer ( ⁇ 2 ) are the same.
  • the specific contents of the ⁇ ⁇ resin ( ⁇ ⁇ 2 ) indicated by reference numerals for the ⁇ ⁇ layer (polyolefin layer) are as shown below.
  • composition of the ⁇ layer ( ⁇ 1 ) and the ⁇ layer ( ⁇ _) is the same.
  • the bond strength between the specimens was determined by cutting a 25 mm wide test piece from the composite material and measuring it in a 90 ° peel test at a peel rate of 300 mm / min in accordance with JISZ 0237. (MNZ 25 mm) was taken as the adhesive strength.
  • the adhesive strength may be measured as described above. If it is not possible to cut out a test piece with a width of 25 mm, cut out a test piece as wide as possible and perform the above measurement on the cut out test piece. The obtained value (mN) is multiplied by (width of 25Z test piece (mm)) to obtain the adhesive strength (mNZ25 mm).
  • the thickness of the composite is as follows.
  • the thickness of the composite material was measured at any 20 points on the vertical cross section in the thickness direction, and the average value was adopted. The thickness was measured using a micrograph and converted to an enlargement magnification to determine each thickness.
  • test piece having a length of 20 cm (length) ⁇ 20 cm (width) ⁇ composite material was cut out from the composite material, and the weight of the test piece (g) was measured. m 2 ) was calculated.
  • test piece similar to the basis weight measurement of the composite material was prepared, the test piece weight (g) was measured, and the test piece volume (cm) obtained by measuring 20 cm (length) ⁇ 20 cm (width) ⁇ the thickness (cm) of the composite material It was determined by dividing the test piece weight (g) by 3 ).
  • HH32 made by Idemitsu Petrochemical Co., Ltd.
  • GPPS general-purpose polystyrene
  • HH30J manufactured by Idemitsu Petrochemical Co., Ltd. (GPPS, melt viscosity 1 230 Pas, density 1.05 g Zcm)
  • MK2111 Polylene-ethylene bronze manufactured by Nippon Polyolefin Block copolymer, melt viscosity 800 Pa, S melting point 16 3 ° C, density 0.9 g Z cm 3 , Vicat softening point 120 ° C or more, semi-crystallization time (10 0 0. C) 10 seconds or less)
  • E250G manufactured by Idemitsu Petrochemical Co., Ltd. (Propylene-ethylene block copolymer, melt viscosity 1570 Pa ⁇ S, melting point 163 ° C, density ⁇ .9 g Z cm 3 , Vicat softening point of 120 ° C or more, half-crystallization time (100 ° C) of 10 seconds or less
  • Modiper A 3100 styrene graft polypropylene, melt viscosity 360 Pas, density 0.94 g / cm 3 )
  • F8188 Polylene-ethylene random copolymer melt viscosity 630 Pa'S (190 ° C), melting point 145.7 C, density 0.9, manufactured by Chisso Corporation) g / cm 3 , Vicat softening point above 120 ° C, half-crystallization time (100 ° C) 25 seconds)
  • J5051HP Polylene-ethylene block copolymer, melt viscosity 260 Pas, melting point 16 ° C, density 0.9 gZ cm 3 , Vicat softening point 15 1 ° C, half-crystallization time (100 ° C) 10 seconds or less
  • Troftec L512 hydrogenated styrene-butadiene styrene block copolymer, melt viscosity 290 Pa ⁇ S, density 0.91 g
  • K Resin KR05 manufactured by Philips (styrene butadiene styrene block copolymer, melt viscosity 1150 Pa'S, density 1. OlgZ
  • melt viscosities given for the present invention have been measured as follows.
  • the above formula (1) was used to calculate the PI value of the alloy layer.
  • When adding a compatibilizer calculate without the compatibilizer. A calculation example in the case of the embodiment is shown below.
  • the viscosity of the P ⁇ component is 731 Pa'S.
  • ⁇ I (viscosity of P S component: 2 0 4 0 X ⁇ ⁇ volume fraction of ⁇ component: 2 7) /
  • Table 9 shows the density (g Z cm 3 ), the thickness of the composite (mm), and the adhesive strength (mNZ 25 mm) of the polyolefin resin layer (Z 1 or Z 2). Table 9 also shows the moldability, mold release and heat resistance of the composite.
  • Polyolefin resin layer has uneven stretching. Releasability ⁇ Good
  • Mold may stick to the mold during mold release Heat resistance ⁇ ⁇ No deformation of container
  • the polyolefin resin (Z1) indicates the surface layer
  • the polyolefin resin layer (Z2) indicates the back layer.
  • the foam layer was heated and kneaded with a prescribed amount of resin and additives from the raw material input port in an extruder with a diameter of 65 mm in the amount shown in Table 10 per 100 parts by weight of resin, and was heated to about 200 ° C.
  • the mixed foaming agent 30% by weight of isobutane and 70% by weight of normal butane was press-fitted into the extruder shown in Table 10 with respect to the resin mixture adjusted to the above, and then the blowing agent-containing molten resin was mixed with a diameter of 9%.
  • the feed was to a 0 mm extruder.
  • the polyolefin resin layer is supplied from an extruder with a diameter of 50 mm
  • the alloy layer is supplied from an extruder with a diameter of 4 Omm to one or both sides of the molten resin for forming a polystyrene resin foam layer, as required.
  • section ⁇ it was combined with the molten resin for foam layer formation and co-extruded.
  • the compatibilizer was added to the alloy layer as needed in the amount shown in Table 10.
  • the extruded cylindrical resin was taken out along a cooled cylinder (mandrel) having a diameter of 200 mm, and then the composite material was wound into a roll.
  • Table 10 shows the specific contents of the foam layer (X), the alloy layer (Y), and the polyolefin resin layer (Zl, Z2) constituting the composite material.
  • the specific contents of the PS resin (polystyrene resin) indicated by reference numerals for the foam layer (X) are as described above.
  • the talc blended with the PS resin is Matsumura Sangyo's High Filler # 12.
  • the specific contents of the PO resin (polyolefin resin) and the compatibilizer with respect to the alloy layer (Y) are as described above.
  • E203 Polylene-ethylene random copolymer, melt viscosity 7500 Pa ⁇ s (190 ° C), melting point 138.5 ° C, vicat softening, manufactured by Chisso Corporation) Point 1 19 ° C, density 0.9 g Z cm 3 , half-crystallization time (100 ° C) 53 seconds)
  • F1188 polypropylene homopolymer, melt viscosity 6.50 Pa ⁇ s (190 ° C), melting point 160.3 ° C, Vicat softening point 1 5 1 ° C, density 0.9 g Z cm 3 , half-crystallization time (100 ° C) 6 seconds)
  • the composite materials obtained in Examples and Comparative Examples were stored in a single-shot molding machine (PL AVA C-FE36 HP type manufactured by Sanwa Kogyo Co., Ltd.). With a partitioning rib that divides it into six equal parts, a rectangular shape with a length of 210 mm, a width of 55 mm, and a depth of 50 mm was attached and vacuum forming was performed for evaluation. In this molding test, all of the 40 dials of the voltage regulator of the upper heater were set to 30 and all of the 6 dials of the lower heater were set to 40. I went.
  • the composite materials obtained in Examples and Comparative Examples were molded into a rectangular container of 210 mm in length and 150 mm in width and 50 mm in depth. 300 ml of hot water at 0 ° C was added, and the mixture was heated in a 500 W microwave oven for 1 minute, and then checked for deformation.
  • Two extruders having a diameter of 65 mm and a diameter of 9 Omm were used in tandem type as extruders for producing a foam layer.
  • an extruder with a diameter of 50 mm was used as the extruder for the polyester resin layer
  • an extruder with a diameter of 40 mm was used for the production of the alloy layer
  • a die with a diameter of 84 mm was used.
  • mm and a cylindrical slit with a gap of 0.5 mm were used.
  • the polyester resin B laminated on the foam layer is extruded by adjusting the resin temperature to 215 ° C with a 50 mm diameter extruder, and the resin constituting the alloy layer is a polystyrene resin F 6 0% by weight and polyester resin G40 0% 0 /.
  • the mixture was extruded from a 40 mm diameter extruder while adjusting the resin temperature to 150 ° C.
  • the resin constituting the alloy layer and the polyester resin were supplied from the foam sheet side in such a manner as to be laminated in this order, and were combined with the foamable resin inside the die and co-extruded.
  • the extruded cylindrical foamed resin was taken out along a cooled cylinder having a diameter of 200 mm, and then cut open to obtain a composite material, which was wound up.
  • the thickness of the foam layer is 1.4 mm
  • the thickness of the alloy layer is 0.04 mm
  • the thickness of the film-like polyester resin is 0.05 mm.
  • a polystyrene resin L with a resin temperature of 260 ° C was extruded from a 65 mm diameter extruder equipped with a 700 mm wide T die on the obtained sheet, and extruded and laminated to perform one side. Then, a composite material in which a 0.15 mm-thick film-like polystyrene resin was laminated and adhered, and a film-like polyester resin was laminated and adhered to one surface of the other side via an alloy layer was obtained.
  • Polystyrene resin F is trade name Styrone H8601, manufactured by A & M Styrene Co., Ltd. and has a melt viscosity of 98 Pas and a vicat softening point of 9 6 ° C, the density is 1. 0 5 g / cm 3 .
  • Polyester resin G is a product name: Biono Ire # 1903, manufactured by Showa High Polymer Co., Ltd., with a melt viscosity of 62 Pas, a melting point of 114 ° C, and a density of 1 . a 2 6 g Z cm 3.
  • Polystyrene resin L is trade name RQ301, manufactured by Denki Kagaku Kogyo Co., Ltd., its melt viscosity is 650 Pas, its vicat softening point is 97 ° C, and its density is 1. is a 0 5 g Z cm 3.
  • the polyester resin B is polyester PETG 6763 from Eastman Chemical Japan Co., Ltd., has a half-crystallization time of 60 minutes or more (100 ° C), and has a melt viscosity of 210 ° C. Polymerization using P aS, density 1.26 g Z cm 3 n ,
  • melcene MX 28 melt viscosity 2770 Pa ⁇ S, density 0.94 g / cm 3 , melting point 117 ° C, east Soichi Co., Ltd. was used.
  • blowing agent ⁇ a butane mixture consisting of 70% by weight of n-butane and 30% by weight of iso-butane was used.
  • polyester resin P manufactured by Nippon Unipet Co., Ltd., has a melt viscosity of RT 543, a half-crystallization time of less than 30 minutes (100 ° C), and unmelted at 190 ° C. unmeasurable, the density 1. 2 6 g / cm 3.
  • Polyester resin P was used in place of polyester resin B as the polyester resin, and the composite material was extruded in the same manner as in the example except that the extruder was extruded at a resin temperature of 270 ° C from a 50 mm diameter extruder. Obtained.
  • the composite material obtained in each of the examples and comparative examples was formed using a single-shot molding machine (PL AVAC-FE36HP type manufactured by Sanwa Kogyo Co., Ltd.) with an opening shape of 150 mm in diameter and a bottom diameter of 1 2. Attach a container mold of 0 mm, depth of 60 mm or 30 mm with a frustoconical shape. Vacuum forming was performed. In this molding test, all 40 dial scales for the upper heater and the voltage regulator were set to 30 and all six dial scales for the lower heater and the voltage regulator were set to 40. I went. The moldability (thermoformability) was evaluated based on the appearance of the obtained molded body.
  • extruders for producing a polystyrene-based resin foam layer two extruders having a diameter of 90 mm and a diameter of 120 mm were connected in tandem.
  • a cylinder with a diameter of 135 mm and a gap of 0.3 mm was used as a c- base using an extruder with a diameter of 65 mm for the production of a polyolefin resin layer.
  • the blowing agent ⁇ is n-butane 70% by weight, is ⁇ I
  • the resin constituting the alloy layers (2) and (3) on both sides of the polystyrene resin foam layer is resin 50% by weight as a polyester resin and resin 50% by weight as a polystyrene resin. 100 parts by weight of the mixture was added with 10 parts by weight of compatibilizer T, and these were added to an extruder having a diameter of 65 mm from an extruder.
  • the resin temperature was adjusted to 0 ° C.
  • the resin constituting the polyester resin laminated on the polystyrene resin foam layer via the alloy layer (2) is resin S, which is extruded at a resin temperature of 200 ° C from an extruder with a diameter of 45 mm. Was adjusted.
  • the polyester resin contains 70% by weight of the resin S. /.
  • the polyolefin resin 3% by weight of resin M was used. This was adjusted to a resin temperature of 170 ° C. by an extruder having a diameter of 65 mm.
  • the resin constituting the two outermost polyolefin resin layers of the composite material was resin M, which was adjusted to a resin temperature of 185 ° C by an extruder having a diameter of 65 mm.
  • the respective resins are merged inside the die and co-extruded to form a polyolefin resin layer, an adhesive layer (1), a polyester resin layer, an alloy layer (2), a polystyrene resin foam layer, an alloy layer (3), and a polyolefin resin.
  • the cylindrical foamed resin laminated in the order of the layers was taken out along a cooled cylinder having a diameter of 335 mm, and then cut open to obtain a composite material, which was wound up. Table 13 shows properties of the obtained composite material.
  • the resin constituting the polyolefin resin layer is resin H (propylene-ethylene block copolymer), and the adhesive layer (1), alloy layer (2), and (3) are yellow.
  • a composite material was obtained in the same manner as in Example 25, except that 4.2 parts by weight of EPS-E40518 manufactured by Pigment Polycarbon Industry Co., Ltd. was added to 100 parts by weight of the mixed resin.
  • the adhesive layer (1), the alloy layers (2) and (3) were mixed with black pigment SBF-T-1683 (carbon black) manufactured by Resinoka Ichi Kogyo Co., Ltd.
  • a composite material was obtained in the same manner as in Example 25 except that 2 parts by weight was added.
  • the resin constituting the polyolefin resin layer is resin E (high-density polyethylene), and the foaming agent A is 0 for the resin kneaded material adjusted to about 200 ° C as the polystyrene resin foam layer.
  • a composite material was obtained in the same manner as in Example 25, except that 0.7 parts by weight was pressed and the density of the polystyrene foam layer was 0.35 g Z cm 3 and the thickness was 0.55 mm.
  • a composite material was obtained in the same manner as in Example 28 except that resin N (high-density polyethylene) was used as the resin constituting the polyolefin resin layer and resin D was used as the polystyrene resin foam layer.
  • resin N high-density polyethylene
  • the open cell ratio was 8 to 20%.
  • Polyester resin S “PESTAG PETG 6763 J” (melt viscosity 2100 Pas, density 1.26 g / c semi-crystallization time 60 minutes or more) manufactured by Yeastman Chemical Japan Co., Ltd.
  • PS resin type A A B B B B D A Type of additive and talc talc talc talc talc talc talc talc Foam layer None
  • Type of PS resin A A D D D and amount (% by weight) 75 75 75 75 70
  • Type of compatibilizer and amount of Y V V Y V X (parts by weight) 25 5 5 25 10 6.25
  • Foam layer (X) 1.12 1.12 1.12 1.12 0.82 1.12 1.12 (Thickness:

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Abstract

L'invention concerne un corps composite renfermant une couche de mousse de résine polystyrénique, une couche d'alliage située sur au moins un coté de cette couche de mousse de résine polystyrénique, et une couche de résine thermoplastique placée sur cette couche d'alliage. La couche de résine thermoplastique renferme une résine choisie entre une résine polyoléfinique et une résine de polyester, la couche d'alliage contenant un mélange d'une résine polystyrénique et d'une résine thermoplastique choisie entre une résine polyoléfinique et une résine de polyester, à condition que la résine thermoplastique de la couche d'alliage soit une résine polyoléfinique lorsque la couche de résine thermoplastique consiste sensiblement en une résine polyoléfinique, et que la résine thermoplastique de ladite couche d'alliage soit une résine de polyester lorsque la couche de résine thermoplastique consiste sensiblement en une résine de polyester. Enfin, la force d'adhérence entre ladite couche de mousse de résine polystyrénique et ladite couche de résine thermoplastique est supérieure ou égale à 980 mN/25 mm.
PCT/JP1999/005996 1999-04-09 1999-10-28 Corps composite renfermant une couche de mousse de resine polystyrenique et une couche de resine thermoplastique WO2000061368A1 (fr)

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JP10325899A JP4059415B2 (ja) 1998-04-24 1999-04-09 ポリスチレン系樹脂発泡体／ポリオレフィン系樹脂多層体
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TWI479178B (zh) * 2010-07-13 2015-04-01 Chien Chin Mai Protective film for optical film

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