WO2001087597A1 - Laminated polystyrene film and process for producing the same - Google Patents

Abstract

A laminated film which comprises a layer (B) (made of an atactic styrene polymer or a resin composition containing the polymer) and superposed on both sides thereof layers (A) (made of a syndiotactic styrene polymer or a resin composition containing the polymer, the styrene polymer having a crystallinity of 20% or higher) and which has a total haze of 10% or lower. The laminated polystyrene film has high transparency and is excellent not only in heat resistance, oil resistance, and mechanical strength but in both of heat processability (thermoformability) and transparency.

Description

 Polystyrene-based laminated film and method for producing the same

Technical field

 The present invention relates to a polystyrene-based laminated film and a method for producing the same, and more particularly, has excellent transparency, heat resistance, oil resistance, etc., and also has good thermal processing suitability (thermoformability).

Police fields that are useful as films, bags, and containers for daily necessities and industrial use

The present invention relates to a styrene-based product, a layer film, and a method for producing the same.

Landscape technology

 Styrene-based polymers having a syndiotactic structure (hereinafter sometimes abbreviated as “SPS”). Films have chemical and physical properties such as mechanical strength, heat resistance, appearance, solvent resistance, and moisture resistance. Because of its superiority, it is used for various applications such as packaging films, bags and containers for foods, drugs, stationery, daily necessities, etc., industrial films and containers such as photographic films, release films, adhesive tapes, and capacitor films. And is expected to be used or used.

 Also, in order to have various functions by having an SPS layer, a laminated film of polyester, polycarbonate, polyamide, and polyphenylene sulfide (Japanese Patent Laid-Open No. 1-262131). Ethylene monobutyl alcohol A laminate with a copolymer (Japanese Patent Application Laid-Open No. 2-192492), a laminated film with a metal thin film (Japanese Patent Application Laid-Open No. 2-143,851), a laminate with poly (vinylidene chloride) (Japanese Patent Application Laid-Open 3-12 65 5 5), a laminate with a rubber-based adhesive (Japanese Patent Laid-Open No. 4-261485), and the like have been proposed.

+ The SFS film used for these various applications and the two- or three-layer laminate using it are heat-resistant, oil-resistant, etc. Excellent thermal properties, but with heat processing suitability (thermoformability) It was broken during thermoforming and had problems such as delamination. Further, a laminate with a rubber-based pressure-sensitive adhesive (Japanese Patent Application Laid-Open No. 4-26185) was apt to warp and was not suitable for thermoforming. In addition, none of these multilayer films was sufficiently transparent. On the other hand, stretched polystyrene films and sheets with an atactic structure are excellent in rigidity, transparency, thermoformability, and heat sealing, and are generally used for applications such as container lids, but have improved heat resistance and oil resistance. Was desired.

 Furthermore, a laminated film of an SPS film and a polystyrene-based polymer (GFPS) having an atactic structure (JP-A-7-112516) has been proposed from the viewpoint of imparting heat sealability. However, the transparency was not always sufficient, and the thermoformability was also insufficient.

 In addition, it has been desired to solve various problems as described below for laminated films.

 In general, a coextrusion method is used for producing a laminated film. When co-extrusion is carried out, it is considered to adjust the fluidity of the resin composition constituting each layer.However, when co-extrusion of the same type of styrene-based polymer such as SPS and GPPS, Since it is considered that the equivalent molecular weight = the same fluidity, it is considered that the molecular weights of the constituent materials should be matched. Even if SPS and GPPS with the same molecular weight were used, it was difficult to obtain a film having uniform physical properties in the width direction due to uneven layer ratio distribution and interface roughness.

 SPS is crystalline and has excellent chemical resistance, so when laminating the stretched film to other substrates, the solvent type of anchor coating (AC) and dry laminating agents is limited to a certain range. Is done. In addition, there is a problem that printing on the SPS layer also limits effective ink types.

Polystyrene, such as GPP S and SPS, has high transparency but is a brittle material. To improve toughness, blends of polystyrene and thermoplastic elastomers and graft polymers such as HIPS have been put to practical use. On the other hand, significantly impairs transparency. Furthermore, even if the toughness is developed by stretching in the SP S / GPP S multilayer stretched film, the orientation of the GPP S layer is relaxed in the heat treatment process, so the toughness of the multilayer film is very low compared to the SPS monolayer film. There was a problem.

 When laminating SPS and GPFS, the extrusion temperature of GPPS is usually around 200 tons, and it is extruded at a temperature at which thermal decomposition does not occur.Therefore, specific antioxidants that do not decompose at high temperatures are added. On the other hand, since SPS is crystalline, it must be extruded at a temperature equal to or higher than its melting point, even though it has the same molecular structure as GPPS, and usually needs to be extruded at 270 to 300 ° C. Therefore, when GPPS is formed into a sheet under the extrusion conditions of SPS, problems such as smoke, decomposition of rolls, and burning of eyes due to decomposition occur. When co-extrusion of SP S and GFP S is required, the extrusion temperature of the SPS must be adjusted from the junction to the die, and the time required for GPPS to be exposed to high temperatures is prolonged. .

 In the case of a multi-layer stretched film such as an SPS / GPP S / SP S configuration, there was a problem that, when heat-treated, the mechanical properties deteriorated because the orientation of the GPP S layer was greatly relaxed. Disclosure of the invention

 The present invention has been made from the above viewpoint, and maintains polystyrene having excellent heat processing suitability (thermoformability) and transparency while maintaining the heat resistance, oil resistance and mechanical strength of conventional SPS. Laminated film and method for producing the same,

 A polystyrene-based laminated film having a uniform appearance in the width direction, having no uneven layer ratio distribution, and no roughened interface, and a good appearance,

3 3 / & ?? 3 layers of the polystyrene-based laminate film with excellent secondary processing properties such as adhesiveness and printability, and its manufacturing method, Inexpensive polystyrene-based precious layer film with excellent transparency, heat resistance, oil resistance, thermoformability, etc., and improved toughness, and method for producing the same

 A polystyrene-based laminated film having improved toughness without impairing the transparency of polystyrene, a method for producing the same,

 A method for producing a polystyrene-based laminated film that prevents decomposition of GFP S during extrusion and has good continuous productivity.

 An object of the present invention is to provide a method for producing a polystyrene-based laminated film having improved toughness while retaining various properties of the polystyrene-based laminated film. As a result of the superposition, it has been found that the above-mentioned object of the present invention can be effectively achieved by a laminated film composed of a specific combination of films having a specific composition and properties, thereby completing the present invention. That is, the gist of the present invention is as follows.

 (1) A laminated film in which the following layer A is laminated on both sides of layer B, wherein the total haze of the laminated film is 10% or less.

 'A layer: a layer composed of a styrene-based polymer having a syndiotactic structure or a resin composition containing the same, wherein the styrene-based polymer has a crystallinity of 20% or more.

 Layer B: a layer made of a styrenic polymer having an atactic structure or a resin composition containing the same.

 (2) The polystyrene-based laminated film according to (1), wherein the ratio of the thickness of each layer of the layer A / layer B / layer A is 1/1/8/1 to 2/1/2.

 (3) The polystyrene-based laminated film according to (1), wherein no adhesive is present between any of the A layer and the B layer.

(4) The layer A has a weight average molecular weight of 150,000 to 300,000, the layer B has a weight average molecular weight of 220,000 or more, Syndiotactic construction The ratio (SP SMw / GPP SMw) of the weight-average molecular weight (SP SMw) of the styrene polymer of the styrene polymer to the weight average molecular weight (GPP SMw) of the styrene polymer of the atactic structure in the B layer is 0.3 to 0. 9. The polystyrene-based laminated film according to the above (1), which is 9.

 (5) The polystyrene-based laminated film according to (1), wherein the deflection temperature under load of the layer B is 80 ° C or more.

 (6) The polystyrene-based laminated film according to (1), wherein the A layer is a composition in which a styrene-based polymer having an atactic structure is added in an amount of 2 to 50% by weight to a styrene-based polymer having a syndiotactic structure. .

(7) B layer is a composition obtained by adding styrene-based polymer of the syndiotactic structure in an amount of 5 0 wt _^0/0 or less of styrene-based polymer of Atakuchikku structure, styrenic polymer of the thin Jiotakuchikku structure The polystyrene-based laminated film according to the above (1), wherein the ratio of the weight-average molecular weight to the weight-average molecular weight of the styrene-based polymer having an atactic structure is 0.3 to 0.9.

(8) Purendo of styrene polymers of styrene polymer 5 0-9 5 weight ⁰ / o and syndiotactic structure of the layer B is Atakuchikku structure or polymer composition you containing the Purendo was 5-5 polystyrene laminate off Irumu according to 0 weight _^0/0 a is the (1).

 (9) The polystyrene-based laminated film according to (8), wherein the molecular weight of the styrene polymer having a syndiotactic structure used for the layer B is equal to or less than the molecular weight of the styrene polymer having an atactic structure.

(1 0) A layer and 2-5 0 weight at least one layer on one diene-based styrene content of more than 50 mol% of styrene or a styrene-O les fin system block or graphene shift copolymer of layer B ⁰ / The polystyrene-based laminated film according to the above (1), which contains ₀ .

(11) The polymer or resin composition that forms the A layer and the polymer or resin composition that forms the B layer The melt viscosity ratio at 290 ° C and a shear rate of 10-'sec- 'is 0.3 to 3, and the polymer or composition is melt-co-extruded and then stretched. And said

The method for producing a polystyrene-based pulp layer film according to (1).

 (12) The layer A has a weight average molecular weight of 150,000 to 300,000, the layer B has a weight average molecular weight of 220,000 or more, The ratio (SF SMw / GPP SMw) of the weight average molecular weight (SP SMw) of the syndiotactic styrenic polymer to the weight average molecular weight (GPP SMw) of the atactic styrenic polymer in the B layer is 0.3. The method for producing a polystyrene-based laminated film according to the above (4), wherein the styrene-based material having a molecular weight of 0.9 to 0.9 is melted at 250 to 300 ° C and co-extruded.

 (13) The method for producing a polystyrene-based or layered film according to (12), wherein the copolyextrusion is followed by cooling and biaxial stretching.

(14) A composition in which a styrene-based polymer having an atactic structure is added in an amount of 2 to 50% by weight ⁰ / o to a styrene-based polymer having a syndiotactic structure, a styrene-based polymer having an atactic structure and, if necessary, The method according to (6), wherein the composition comprising a styrenic polymer having an tactic structure is melt co-extruded, cooled, and biaxially stretched.

(1 5) styrenic polymer of crystallinity of 2 0% or more syndiotactic structure or polymer composition containing the polymer and Atakuchikku styrene polymer 5 0-9 5 weight structure ⁰ / The polystyrene according to the above (8), which is stretched after melt co-extrusion using a blend of ₀ and a styrene polymer having a syndiotactic structure or a polymer composition containing 5 to 50% by weight of the blend. A method for producing a laminated film.

(16) The method for producing a polystyrene-based laminated film according to (15), wherein the molecular weight of the styrene-based polymer having a syndiotactic structure is not more than the molecular weight of the styrene-based polymer having an atactic structure.

(17) Syndiotactic styrene polymer or a composition containing this polymer, and atactic styrene polymer or a composition containing this polymer At least one of these compositions contains a styrene-gen-based or styrene-olefin-based block or graft copolymer having a styrene content of 50 mol% or more in an amount of 2 to 50% by weight ⁰ / o. The method for producing a polystyrene-based laminated film according to the above (10), wherein these are melt-coextruded, then cooled and stretched.

(18) 5% weight loss in syndiotactic styrene polymer or polymer composition containing this polymer, and atactic styrene polymer or polymer composition containing this polymer temperature using the the 140 ° C or more antioxidants 0.00 1 to 0.5 wt _^0/0 added styrene-based material, manufacturing method of the polystyrene-based laminate film to melt coextrusion at 250 to 300 ° C.

(19) An antioxidant having a 5% weight loss temperature of 240 ° C or more is added to the styrene-based polymer having the atactic structure or the polymer composition containing the polymer in the amount of 0.001 to 0.5 weight ⁰ / o A three-layer structure in which a layer made of a styrene-based polymer having a syndiotactic structure or a polymer composition containing this polymer is laminated on both sides of a layer made of the added styrene-based material, and the layer ratio is 1 (18) The method for producing a polystyrene-based laminated film according to the above (18), wherein the ratio is 18/1 to 2/1/2.

 (20) The method according to (18) or (19), wherein the co-extrusion is followed by cooling and biaxial stretching.

 (21) a styrene polymer having a syndiotactic structure having a molecular weight of 150,000 to 300,000 or a composition containing this polymer (A);

Melt co-extrusion with a styrene polymer having an atactic structure of 000 or more or a composition containing this polymer (B) at 250-300 ° C, co-stretching, and heat treatment at a temperature of 160 ° C or less Of producing a polystyrene-based laminated film.

(22) as a composition (A), said that use those obtained by adding the styrene polymer of the syndiotactic structure of a styrene-based polymer of § tactic structures at a rate from 2 to 50 weight _^0/0 (2 1 ). (2 3) as a composition (B), using a plus at the rate of § evening 5 styrenic polymer Shinjio evening Kuchikku structure styrenic polymer Kuchikku structure 5 0 wt ^0/6 the ( 21. The method for producing a polystyrene-based laminated film according to 1). BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described.

 The polystyrene-based laminated film of the present invention is composed of an A layer and a B layer, which will be described later, and is a laminated film in which the A layer is laminated on both sides of the B layer. % Or less.

 By forming the A layer and the B layer having the specific composition as the A layer / B layer / A layer, the transparency and the like are excellent, and at the same time, the heat processing suitability (thermoformability) is excellent. It demonstrates. The term “excellent in thermal processing suitability (thermoformability)” as used in the present invention means that the film before thermoforming or the film does not warp during preheating (flatness), does not break during thermoforming, and does not cause problems such as delamination. A property that does not cause warpage in molded products.

 Hereinafter, the content of each layer constituting the laminated film of the present invention, the layer constitution, the production method of the laminated film, and the like will be described in detail.

1. Layer A

 The layer A of the present invention is a layer composed of SPS or a resin composition containing the same.

A syndiotactic structure in SPS refers to a syndiotactic structure in which a phenyl group, which is a side chain, is alternately located in the opposite direction to the main chain formed from carbon-carbon bonds. are those having, its Takutishite I one is quantified by nuclear magnetic resonance method using carbon isotope ^{(1 3} C- NMR). ^The tacticity measured by ¹³ C-NMR is the abundance ratio of a plurality of continuous structural units.For example, two units are diat, three units are triads, and five units are triads. In general, SPS referred to in the present invention is usually 75% or more in racemic diat, preferably 85% or more, or 30% or more in racemic pen, preferably Polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly '(halogenated alkylstyrene), poly (alkoxystyrene), poly (bul benzoate), having a syndiotacticity of 50% or more These hydrogenated polymers and mixtures thereof, or copolymers containing these as a main component, are referred to. Here, the poly (alkylstyrene) includes poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (monobutyl styrene), poly (phenylstyrene), poly (vinylnaphthalene). ), Poly (butylstyrene), etc., and poly (halogenated styrene) includes poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like. Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

 Among these, particularly preferred styrene polymers include polystyrene, poly (P-methylstyrene), poly (m-methylstyrene), poly (ethylstyrene), poly (dibutylbenzene), and poly (F-butylstyrene). Examples include poly (p-chlorostyrene), poly (m-chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units.

Such SPS can be prepared, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent to obtain a styrene-based monomer (the styrene-based (Corresponding monomers) can be produced (Japanese Patent Laid-Open No. 62-187708). Further, poly (halogenated alkylstyrene) is disclosed in Japanese Patent Application Laid-Open No. The hydrogenated polymer can be obtained by the method described in Japanese Patent Application Laid-Open No. Hei 11-87505.

 Further, the comonomers in the styrene copolymer include olefin monomers such as styrene as described above, gen monomers such as butadiene and isoprene, cyclic genmonomers-methyl methacrylate, maleic anhydride, and atalononitrile. And polar vinyl monomers.

In particular, a styrene-based polymer having a styrene repeating unit of 80 to 1 Q0 mol ⁰ / o and a p-methylstyrene repeating unit of 0 to 2 mol% is preferably used.

 In the present invention, the weight average molecular weight of SFS is preferably 150,000 or more and 300,000 or less. Here, if the weight average molecular weight is less than 150,000, the mechanical properties are degraded, and if it exceeds 300,000, the layer ratio distribution unevenness may occur in the width direction. Furthermore, as for the molecular weight distribution, there is no restriction on the width thereof, and various types can be applied.

The high degree of the SPS, 7 0-1 0 0 mass _^0/0 to A layer in the present invention, further 8 0-1 0 0 mass _^0/0, especially 9 0-1 0 0 mass _^0/0 contained Preferably.

A layer of the styrene-based polymer (GPPS) 2-5 0 weight _^0/0 Atakuchikku structure styrenic polymer of syndiotactic configuration (SFS), preferably 5 to 3 5 by weight ⁰ / o, especially preferably it is made of 1 0-3 0 weight _^0/0 added compositions. Here, when the addition amount of GPPS is less than 2% by weight, the secondary workability is not improved, and when it exceeds 35 Q / o, the gloss tends to decrease due to a solvent or the like, and exceeds 50% by weight. This causes rough skin.

A layer syndiotactic styrene polymer of Atakuchikku structure styrenic polymer (SPS) structure (GPPS) 2-5 0 weight _^0/0, preferably 5-3 5 by weight ⁰ / o, especially preferably It is preferable to add 10 to 30 weight ⁰ / o. Here, when the amount of GPPS added is less than 2% by weight, no improvement in the secondary workability is observed. When the amount exceeds 35%, the gloss tends to decrease due to solvents and the like, and when it exceeds 50% by weight, the skin becomes rough. Occurs You.

The SPS is 5 0-9 8 weight ⁰ / o to A layer in the present invention, further 6 5-9 5 wt%, in particular 7 0-1 9 wt _^0/0 preferably contained.

As the layer A of the present invention, a thermoplastic resin other than SPS, a thermoplastic elastomer, a compatibilizing agent, and the like can be blended with the above-mentioned SPS as long as its purpose is not impaired. These formulations are 0-3 0 mass layer A _^0/0, more 0-2 0 weight ⁰ / o, may be blended in a range especially of 0-1 0% by weight.

 Further, the layer A may contain various additives as required. Hereinafter, these compounding agents and additives will be described.

 (1-1) Thermoplastic resins other than SPS

Thermoplastic resins other than SPS that may be used in the present invention include linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, and block polypropylene. , Random polypropylene, polybutadiene, polybutadiene, poly4-methylpentene, cyclic polyolefins and polyolefin resins represented by these copolymers, atactic polystyrene, isopolystyrene, HIPS, ABS, AS Styrene-methacrylic acid copolymer, styrene-methacrylic acid-alkyl ester copolymer, styrene-methacrylic acid'glycidyl ester copolymer, styrene-acrylic acid copolymer, styrene-acrylic acid-alkyl ester Copolymerization Polystyrene resins represented by styrene-maleic acid copolymer, styrene-fumaric acid copolymer, polyester resins such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide 6, polyamide 6, It can be arbitrarily selected from known resins such as polyamide-based resins such as 6, polyphenylene ether, and PFS. These thermoplastic resins can be used alone or in combination of two or more. (1-2) Thermoplastic elastomer

 Specific examples of the thermoplastic elastomer that may be used in the present invention include, for example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, Chlorohydrin rubber, styrene-butadiene block copolymer (sSBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SB S), hydrogenated styrene rubber Monostyrene block copolymer (SEB S), styrene monoisoprene block copolymer (SIR :), hydrogenated styrene monoisoprene block copolymer (SEP), styrene-isoprene monostyrene block copolymer (SIS), hydrogenated styrene Styrene rubbers such as styrene block copolymers (SEPS), and ethylene rubbers such as ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), and linear low-density polyethylene elastomers; or Butadiene-acrylonitrile styrene-core shell rubber

(AB S), Methyl methacrylate butadiene-styrene-core-shell rubber (MBS), Methyl methacrylate-butyl acrylate-styrene-core-shell rubber (MAS), octyl attarile-butadiene-styrene-core-shell rubber (MAB S), Core-shell-type particle-like elastic materials such as alkyl acrylate-butadiene-acrylonitrile-styrene-core-shell rubber (AABS), butadiene-styrene-core-shell rubber (SBR), and siloxane-containing core seal rubber such as methyl methacrylate-butyl acrylate-siloxane. Or modified rubbers thereof. These can be used alone or in combination of two or more ^

 (1-3) Compatibilizer

The compatibilizer that may be used in the present invention is, for example, a copolymer containing a styrene structure, and the styrene structure in the molecule is 40 mol ⁰ / o or more, preferably 50 mol% or more. It is a polymer containing.

Specific examples of such a compatibilizer include, for example, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), Hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer Polymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), and the like. Mel All these also styrene structure polymer containing 50 mole ⁰ / o or more.

 (1-4) Various additives ''

①Anti-blocking agent (AB ij)

 Examples of the antiblocking agent include the following inorganic particles or organic particles.

 '' Inorganic particles include oxides, hydroxides, and sulfides of Group IA, IIA, IVA, VIA, VIIA, VIII, IB, IIB, IIIB, and IVB elements , Nitrides, halides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, succinates and their hydrates, mainly Composite compounds and natural mineral particles.

Specifically, compounds of Group IA elements such as lithium fluoride, borax (sodium salt hydrate), magnesium carbonate, magnesium phosphate, magnesium oxide (magnesia), magnesium chloride, magnesium acetate, magnesium fluoride, titanate Magnesium, magnesium silicate, magnesium silicate hydrate (talc), calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum), calcium acetate, calcium terephthalate, calcium hydroxide, calcium silicate, calcium fluoride Shim, calcium titanate, strontium titanate, barium carbonate, phosphoric acid Group IIA element compounds such as lithium, barium sulfate, and sulfite, titanium dioxide (titania), titanium monoxide, titanium nitride, zirconium dioxide (zirconia), zirconium monoxide, and other group IVA element compounds, molybdenum trioxide, Group VIA element compounds such as molybdenum and molybdenum sulfide; Group VIIA element compounds such as manganese chloride and manganese acetate; Group VIII element compounds such as cobalt chloride and cobalt acetate; Group IB element compounds such as cuprous iodide Group IIB element compounds such as aluminum oxide, zinc oxide, zinc acetate, etc .; Group IIIB element compounds such as aluminum oxide (alumina), aluminum hydroxide, aluminum fluoride, and alumina silicate (alumina silicate, porphyrin, porphyrin), silicon oxide (Silica, silica gel), graphite, graphite, graphite, IVB of glass, etc. Element compound, force one null stone, kainite, mica (My force, Kinunmo) include particles of natural minerals, such Bairosu ore. Here, the average particle size of the inorganic particles used is preferably from 0.1 to 1 Om.

 Examples of the organic particles include Teflon, melamine resin, styrene'divinylbenzene copolymer, ataryl resin silicone, and cross-linked products thereof.These AB agents may be used alone or in combination of two or more. Can be used.

 ② Antioxidant

 The antioxidant can be arbitrarily selected from known ones such as phosphorus, phenol and zeolite. These antioxidants can be used alone or in combination of two or more. Furthermore, preferably, 2- [1-hydroxy-3,5_di-t-pentylphenyl) ethyl] 14,6-di-t-pentylphenyl acrylate is also included.

 ③ Nuclear agent

The nucleating agents include metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate) and methylenebis (2,4-di-tert-butylphenol). Any known metal salt of phosphoric acid, such as sodium phosphate, talc, phthalocyanine derivative and the like can be arbitrarily selected and used. These nucleating agents can be used alone or in combination of two or more.

 ④Plasticizer

 As the plasticizer, any known plasticizer such as polyethylene glycol, polyethylene glycol, polyethylene bis stearamide, phthalic acid ester, polystyrene oligomer, polyethylene oxide, and silicone oil can be used. These plasticizers can be used alone or in combination of two or more.

 ⑤Release agent

 The release agent can be arbitrarily selected from known materials such as polyethylene wax, silicone oil, long-chain ruponic acid, and long-chain ruponic acid metal salt. These release agents can be used alone or in combination of two or more.

 ⑥Process oil

In the present invention, in order to improve the elongation, it is preferable to further blend a process oil having a kinematic viscosity at 40 ° C. of 15 to 600 mm ² Zs.

 Process oils are roughly classified into paraffinic oils, naphthenic oils, and aroma oils depending on the type of oil. Among them, the total number of carbon atoms related to paraffins (straight chain) calculated by the η-d-M method Paraffinic oils having a percentage of carbon number of 60% Cp or more are preferred.

As the viscosity of the process oil, the kinematic viscosity at 40 ° C. is preferably from 15 to 600 mm ² / s, and more preferably from 15 to 500 mm ² / s.

If the kinematic viscosity of the process oil is less than 15 mm ² / s, it has the effect of improving elongation, but the boiling point is low and it is melted and kneaded with SPS, and white smoke, gas burning, roll adhesion, etc. Cause If the kinematic viscosity exceeds 60 O mm ² / s, the burning of white smoke gas is suppressed, but the effect of improving elongation is poor. These process oils can be used alone or in combination of two or more.

The above-mentioned various addition amounts are preferably 0 to 3 masses in the A layer, if necessary. / ₀ , more preferably in the range of 0 to 1.5% by mass.

 The layer A of the present invention has the above composition, and the styrene-based polymer constituting the layer has a crystallinity of 20% or more, preferably 25% or more, and more preferably 30% or more. Must be at least%. Here, if the crystallinity is less than 20%, heat resistance and oil resistance may not be sufficient.

 The method for increasing the crystallinity of the styrene-based polymer constituting the layer A to 10% or more can be achieved, for example, by adjusting the stretching and heat treatment conditions in the method for producing a laminate described below. The crystallinity is the crystallinity of the syndiotactic polymer contained in the layer A, and can be measured by a differential scanning calorimeter.The two A layers present on both sides of the layer B are: The compositions and properties may be the same, but may be different from each other within the above ranges.

 2. Layer B

 As the layer B of the present invention, a layer made of a styrene-based polymer having an atactic structure (hereinafter, sometimes abbreviated as “PS”) or a resin composition containing the same is used.

The FS used in the present invention is a styrene-based polymer industrially obtained by radical polymerization by a method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Polystyrene obtained by such radical polymerization usually has an atactic structure and does not have stereoregularity. In addition, polystyrene having an atactic structure referred to herein is a polymer composed of one or more aromatic vinyl compounds or one or more other vinyl monomers copolymerizable with one or more aromatic vinyl compounds. Copolymers, these It may be a hydrogenated polymer of a polymer, or a mixture thereof.

 Here, aromatic vinyl compounds include styrene, α-methylstyrene, methylstyrene, ethylstyrene, isopropylstyrene, butyl styrene, phenylstyrene, vinylstyrene, chlorostyrene, bromostyrene, fluorostyrene, and chloromethylstyrene. , Methoxystyrene, ethoxystyrene and the like, and these are used alone or in combination of two or more. Of these, preferred aromatic vinyl compounds are styrene, ρ-methylstyrene, m-methylstyrene, ethylstyrene, and p-overnight-shary-butylstyrene.

 Other copolymerizable vinyl monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, methyl acrylate, propyl acrylate, butyl acrylate, amide acrylate, and hexyl acrylate. Acrylate, alkyl acrylate such as 2-methylhexyl acrylate, cyclohexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octyl decyl acrylate, phenyl acrylate, benzyl acrylate, etc., methyl methacrylate , Ethyl methyl acrylate, butyl methacrylate, amyl meth acrylate, hexyl meth acrylate, octyl methacrylate, .2 ethyl ethyl acrylate, cyclohexyl methacrylate Methacrylic acid alkyl esters such as dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, maleimide, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimi And N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N- (p-bromophenyl) maleimide.

 As the GPPS, those having a weight average molecular weight of 220,000 or more are preferred. If the weight average molecular weight is less than 220, 000, uneven layer ratio distribution may occur in the width direction during coextrusion.

As the B layer of the present invention, other thermoplastics may be added to the above PS as long as the purpose is not hindered. It may be blended with a thermoplastic resin, a thermoplastic elastomer, a compatibilizer, and, if necessary, various additives and lubricants. For these specific examples, those described above for the layer A can be used. The same applies to the mixing ratio.

 However, other thermoplastic resins, excluding atactic polystyrene, isotactic polystyrene, and HIPS, which were exemplified in (111), were replaced by SPs not found in (111). S is included.

 The layer containing PS as a main component preferably contains 70% or more, preferably 80%, and more preferably 9 OQ / o or more of the styrene-based polymer component. If the styrene-based polymer component is too small, the transparency after lamination may deteriorate, or the adhesion to the layer containing SPS as a main component may be insufficient, and delamination may occur during thermal processing.

The multilayer film of the present invention is preferably composed of a layer A composed of SPS or a composition containing SPS and a layer B composed of GPPS or a composition containing GPPS, The ratio (SP SMw / GPP SMw) of the average molecular weight (SPSMw) to the weight average molecular weight (GPP SMw) of the above-mentioned GPP S is preferably 0.3 to 0.9. Here, even if the ratio of SP SMw / GPP SMw is less than 0.3 or more than 0.9, uneven layer ratio distribution may occur in the width direction. the SPS consists composition was added at a rate of 50 weight _^0/0 or less, the ratio of heavy weight average molecular weight of the styrene polymer having a weight average molecular weight / Atakuchikku structure of the SPS is at 0.3 to 0.9 It is preferable from the viewpoint of thermoformability. Further, it is preferable that GPPS is contained at 50% by weight or more, preferably 55% by weight or more. When the GPPS is less than 50% by weight, there arises a problem that the thermoforming of the multilayer sheet and the multilayer stretched film becomes insufficient.

Further, in the multilayer film of the present invention, the GPPS layer preferably has a deflection temperature under load of 80 ° C. or more measured in accordance with JISK7207. If the load deflection temperature is less than 80 ° C, the amount of plasticizer added is large, so the SF S extrusion temperature Then, there is a problem that there is much smoke.

As the layer B of the laminated film of the present invention, a layer composed of a blended material comprising GPPS 50 to 95% by weight ⁰ / o and SPS 5 to 50% by weight or a polymer composition containing this blend is used. You may. Now the content of the SPS is less than 5 weight _^0/0, toughness ¾ £ improve can not be obtained, also when more than 5 0% by weight, the thermoformability may be insufficient.

 In this case, it is preferable that the molecular weight of the SPS used for the layer B is equal to or less than the molecular weight of the GPPS, and the same SPS used for the layer A can be used. Here, the weight average molecular weight of the SPS used in the layer B is preferably 2 times or less, more preferably 1.5 times or less, and more preferably 1.2 times or less the SPS used in the layer A. Particularly preferred.

 In at least one of the A layer and the B layer in the present invention, a styrene-gen-based or styrene-one-year-old olefin-based block or graft copolymer having a styrene content of 50 mol% or more is preferably 50% by weight, preferably 50% by weight. A material containing 5 to 30% by weight may be used.

Here, examples of the styrene-gen-based or styrene-olefin-based block copolymer or graft copolymer include styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, and styrene-isoprene random copolymer. Copolymer, hydrogenated styrene-isoprene random copolymer, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB, SEBC), styrene-butadiene-styrene block copolymer Polymer (SB S), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene Isoprene-styrene block copolymer (SIS), water Styrene-isoprene-styrene block copolymer (SEPS), styrene-ethylene copolymer, styrene Examples include a propylene copolymer, an ethylene-styrene graft copolymer, a propylene-styrene copolymer, an EFDM-styrene graft copolymer, or a modified product thereof. Of these, styrene-olefin propylene block copolymer and styrene-one-year-old olefin triple block copolymer are particularly preferable. Specifically, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butene diene block copolymer (SEB, SEBC), styrene-butadiene-styrene block copolymer (SB S), hydrogenated Styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), or a modified product thereof is preferably used.

In the present invention, there is provided a styrenic one diene-based or Suchirenore fin-based block or graft copolymers of the above, a styrene content of 5 0 molar _^0/0 or more is preferable. If the styrene content is less than 50 mol%, poor dispersion results and transparency is reduced.

The amount of such a block or graft copolymer is such that it is contained in an amount of 1 to 50% by weight, preferably 5 to 30% by weight, in the composition constituting the layer into which the block or graft copolymer is to be incorporated. I do. This amount is less than 2 wt%, no effect in improving the toughness, it exceeds 5 0 weight _^0/0, which may reduce the heat resistance, chemical resistance.

In the present invention, GF PS or GF PS-containing composition 5% weight loss temperature 2 4 0 ° C over 0.0 antioxidants 0 1 to 0.5 wt ⁰ / o may be used by adding . In here, the addition amount of the antioxidant is less than 0.0 0 1 weight _^0/0, occurs decomposition of the GPP S layer, smoke, there is a generation of eye catcher two like. If it exceeds 0.5% by weight, coloring and yellowing may occur due to the antioxidant.

The 5% weight loss temperature was measured using a thermal analyzer (PerkinElmer). The temperature was raised at a heating rate of 20 ° C./min in an elementary atmosphere, the weight loss rate was measured, and the temperature at the time of 5% weight loss was defined as this temperature. .

As the antioxidant, if 5% weight loss temperature 24 0 ° C or higher is not particularly restricted, for example, Sumitomo Chemical Co., Ltd. S urn i 1 izer GS (N 2 5% under Weight loss temperature 27 O), Penyu erythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Chemical Corporation, trade name I RGANOX 101 0) : 5% weight loss temperature under N 2 335 ° C) and PEP 36 manufactured by Adeka Gas Chemical Co., Ltd. (5% weight loss temperature under N ₂ 332 ° C).

 In the present invention, the above-mentioned antioxidant-added GPPS is mixed with other thermoplastic resins, thermoplastic elastomers, compatibilizers, and other additives as long as the object of the present invention is not impaired. Various additives may be blended. For these specific examples, those described above for the SPS layer can be used. The same applies to the mixing ratio. However, atactic polystyrene, isotactic polystyrene, and HIPS exemplified in U-1) are excluded from other thermoplastic resins, and instead of this, SP (1-1) does not have S is included.

 The layer containing GPFS as a main component preferably contains 70% or more, preferably 80%, and more preferably 90% or more of a styrene-based polymer component. If the amount of the styrene-based polymer component is small, the transparency after lamination may be deteriorated, or the adhesion to the layer mainly composed of SPS may be insufficient, and delamination may occur during thermal processing.

 The polystyrene-based laminate film is obtained by co-extrusion of the above-mentioned SPS or SPS-containing composition (A) and GPPS or GPPS-containing composition (B) at 250 to 300 C, and after co-stretching. May be manufactured by heat treatment at a temperature of 16Οΐ or less

3. Layer structure of laminated film The laminated film of the present invention is composed of the A layer and the B layer. The ratio of the layer thickness of the A layer / B layer / A layer is 1/1/8 / 1-2 / 1/2. It is preferable that the ratio be 1/1/8/1 to 3/2/3, particularly 1/18/1-1/1/1. Here, if the layer A is too thin, problems tend to occur in the heat resistance and oil resistance of the laminated film, and if the layer A is relatively thick, problems tend to occur in the heat processability of the laminated film.

 Further, the thickness of the A layer is preferably 1 to 500 m, more preferably 1 to 400 m, and particularly preferably 1 to 300 iim. If the A layer is less than 1 m, problems tend to occur in the heat resistance and oil resistance of the laminated film, and if it is 500 m or more, problems tend to occur in the thermal workability of the laminated film. 4. Total haze of laminated film

 The total haze of the laminated film composed of layer A / layer B / layer A of the present invention is a styrene-based laminated film having a total haze of 10% or less, preferably 8% or less, and more preferably 6% or less. If the total haze exceeds 10%, the transparency and transparency of the film are not sufficient, and the object of the present invention cannot be achieved.

 The total haze of the laminated film can be reduced to 10 or less by appropriately adjusting the composition of each layer, the thickness ratio of each layer, and the lamination conditions, stretching conditions, and heat treatment conditions.

 5. Manufacturing method of laminated film

 The laminated film of the present invention can be produced by various methods conventionally used, and the polymer or resin composition to be the A layer and the polymer or resin composition to be the B layer are co-pressed, and then co-pressed. Efficient production can be achieved by using a stretching method. The co-extrusion method is not particularly limited, but may be any of a feed block method and a multi-manifold method, and a die such as a coat hanger die, a T-die, and an annular die can be used.

After melt coextrusion, after cooling and co-stretching, the crystallinity of layer A is improved and transparency is developed. As a method of co-stretching, for example, uniaxial stretching, simultaneous biaxial stretching, sequential biaxial stretching, and a multi-stage stretching method combining these can be used. . Among them, it is preferable to use a simultaneous or sequential biaxial stretching method in the present invention. In this case, the area stretching ratio is preferably 3 to 20 times, more preferably 5 to 10 times. The co-stretching temperature is preferably 90 to 200 ° C, more preferably 90 to I50 ° C. After the co-stretching, it is preferable to perform a heat treatment, preferably under a tension, preferably at 100 to 270 ° C, more preferably at 150 to 270 ° C, and more preferably at 1 to 3 ° C. It may be performed for 00 seconds, more preferably 1 to 60 seconds.

 According to the above method, a laminated film having excellent interlayer adhesion and higher transparency can be produced without using an adhesive.

The preferred method for producing the laminated film of the present invention is as described above. The polymer or the resin composition to be the A layer and the polymer or the resin composition to be the B layer have a shear rate of 10 ° C. The melt viscosity ratio (melt viscosity of layer A) / (melt viscosity of layer B) at ¹ sec ′ is preferably from 0.3 to 3, and more preferably from 0.5 to 2. If the ratio of the melt viscosities of both is less than 0.3 or more than 3, the interface of each layer after co-extrusion becomes coarse, and it may be difficult to obtain the desired transparent laminate.

 In addition, as a method other than the above method, a single film may be prepared and laminated using an adhesive.

 6. Applications of laminated film

 The use of the laminated film of the present invention is not particularly limited and can be widely used, but since it has the above-mentioned properties, it can be used for packaging films, bags and containers for foods, medicines, stationery, daily necessities, release films, adhesive tapes, and the like. It is particularly useful for industrial films and containers such as condenser derivatives. Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Hereinafter, Production Examples 1 to 2, Examples 1 to 4, and Comparative Examples 1 to 9 will be described. -Method of measuring physical properties of film ① Ratio of layer thickness to layer thickness

 A polarizing microscope photograph of the cross section of the film was taken, and the thickness of each layer was measured. The ratio of the layer thickness was calculated from the thickness of each layer.

 ② Crystallinity

The laminated film was calculated by the following equation using the _{enthalpy of} fusion (AHf) measured by a differential scanning calorimeter at a heating rate of 20 ° C / min and the enthalpy of cold crystallization (AH _Tcc ).

Crystallinity (%) = 100 X (AHf — AI-I _Tc ) / (53 (J / g) x SPS content ratio in layer)

 ③ All haze

 The measurement was performed in accordance with the JIS K7105 method.

 ④Tensile modulus, breaking strength

 The measurement was performed according to JIS Z1702.

 ⑤Film impact

 Using a film impact tester made by Toyo Seiki (Pendulum type), the impact head was measured at 1/2 inch (1.27 cm).

 ⑥Surface heat resistance

 Using a film piece, a heat seal test was performed in accordance with JIS Z 1707, and the upper limit temperature of the surface layer (the SPS / PS laminate was not changed in appearance) was measured.

油 Oil resistance

 MCT oil was applied to the film surface (SPS / PS laminate for SPS side), and the change after 30 minutes at 80 ° C was measured. The measurement results were displayed according to the following criteria.

 〇: Haze value 10 Less than / 6,

 X: dissolution or haze value; 10% or more

⑧ Thermoformability (thermal processing suitability) Using a thermoforming machine manufactured by Asano Seisakusho, plug-assist vacuum and pressure forming is performed at a sheet heating temperature of 150 to 200 ° C and a mold temperature of 660 ° C. (5 times magnification) was evaluated.

 〇: Good container shape is possible in both appearance and shape

 X: Any failure such as breakage during molding, container warpage, or delamination (delamination) occurred. SPS, compounding agents and additives used in non-manufacturing examples

 -Styrene-based styrenic polymer (SPS-3)

 Weight average molecular weight 400,000, syndiotacticity (racemic bendat) 97% SPS

 • Atactic styrene polymer (PS-1)

 Idemitsu Petrochemical HH32 (GPP S)

 • Atactic styrene polymer (PS-2)

 Idemitsu Petrochemical HH32 (GPP S) ''

 '' Polyethylene terephthalate (PET)

 Mitsubishi Rayon Diamond MS 5 2 3

 Polyphenylene Sulfide (FPS)

 Intrinsic viscosity [7?] = 0.28 d 1 / g

 • Bisphenol A type polycarbonate (PC)

 Idemitsu Petrochemical Idemitsu Polycarbonate A3 0 0

 -Lubricant 1

 Aluminosilicate (Mitsuzawa Chemicals, Shilton AMT 08)

 • Antioxidants 1

 Penyu erythrityl-tetrakis [3- (3,5-di-t-butyl_4-hydroxyphenyl) propionate], IRGANOX 1010 (manufactured by Ciba Chemical Co., Ltd.)

Preparation of polymerization catalyst Pour toluene, triisobutylaluminum 3.8 mmo1, methylaluminoxane 16.8 mmo1, and oxyhydrofluorenyltitanium trimethoxide 0.15 mm01 into a well-dried and purged vessel. , And the Ti concentration was adjusted to 3 mmo 1/1. Each component was stirred for 1 hour after mixing, and used as a catalyst. Production Example 1: Production of styrene-p-methylstyrene copolymer (SPS-1) 4.7 kg of styrene, 0.3 kg of paramethylstyrene, and triethylaluminum were placed in a well-dried and nitrogen-substituted reactor. Styrene / triethylaluminum = 350, 100/100, and the mixture of well-stirred rostyrene, paramethylstyrene, and triethylaluminum was heated to 73 ° C. 21 ml of the prepared catalyst was added to the mixture to initiate polymerization. One hour later, polymerization was stopped by adding methyl alcohol. The obtained polymer was washed with methanol and dried at 200 ° C. for 2 hours. The yield was 1210 g and the weight average molecular weight was 263,000. The content of paramethylstyrene in the obtained polymer was measured using ¹ H-NMR, and was found to be 5.9 mo 1%.

Production Example 2: Production of styrene homopolymer (SPS-2)

 5 kg of styrene and triethylaluminum were charged into a sufficiently dried and purged nitrogen reactor so that styrene / triethylaluminum = 350, 0000/100, and stirred sufficiently. After heating the mixture of styrene and triethylaluminum to 80 ° C., 21 ml of the catalyst prepared above was added to the mixture to initiate polymerization. One hour later, methanol was added to terminate the polymerization. The obtained polymer was washed with methanol and dried at 200 ° C. for 2 hours. The yield was 230 g and the weight average molecular weight was 207,000. .

Example 1

The SFS-1 obtained in Production Example 1 was mixed with 1,000 ppm of lubricant-1 and 3,000 ppm of antioxidant-1, and after melt extrusion at 300 ° C, pellet And The melt viscosity at 300 ° C and a shear rate of 10-1 sec-'is ¹⁰⁰ PaS I got it. PS-1 (290 ° C, shear rate 10—sec- ¹ melt viscosity: 500 Pa · S) was prepared as an atactic styrene polymer. Each of these two materials was extruded at 300 ° C with a 300ΙΉΓΩΦ single screw extruder and at 260 ° C with a 4ΟιηιηΦ single screw extruder, and the feed block and coat were set at 300 ° C. It was co-extruded through a hanger die and cooled by a cooling roll at 85 ° C to obtain a three-layer unstretched sheet of A layer / B layer / A layer. This unstretched three-layer sheet is continuously stretched 3.4 times in the longitudinal direction at 105 ° C, and then stretched 3.8 times in the transverse direction at 150 ° C. Heat treatment was performed for 10 seconds while relaxing 5% in the width direction. The physical properties of the obtained three-layer stretched film were measured, and the results are shown in Table 1. However, in Table 1, the blending of the additives is omitted.

Example 2

 A laminated film was prepared in the same manner as in Example 1 except that the extrusion amount was adjusted and the thickness of each layer was changed. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1.

Example 3

 The three-layer stretched film was obtained in the same manner as in Example 1 except that the extrusion amount and the take-up speed of the unstretched sheet were adjusted, the thickness of each layer was changed, and no heat treatment was performed. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1.

Example 4

The SPS—2 obtained in Production Example 2 (290 ° C., melt viscosity at a shear rate of 10— ′ sec ¹ 60 OP a · S) and FS—2 (atactic styrene polymer) 2 9 0 ° C, using a shear rate of 1 0- ¹ sec ¹ melt viscosity 3 0 0 P a · S) , the other to change the thickness of each layer was adjusted extrusion rate in the same manner as in example 1 3 A layer stretched film was obtained. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1.

Comparative Example 1

Extruded in the same manner as in Example 1 except that SP S-1 was not used. A single-layer (only layer B) stretched film having a thickness of 12 was prepared. The physical properties of the obtained film were measured, and the results are shown in Table 1.

Comparative Example 2

 Except that PS-1 was not used, a syndiotactic styrene-based polymer monolayer (only layer A) having a thickness of 12 m was prepared in the same manner as in Example 1. The physical properties of the obtained film were measured, and the results are shown in Table 1.

Comparative Example 3

 A 200-μm-thick stretched film of a single layer of syndiotactic styrene-based polymer (only layer A) was prepared in the same manner as in Example 3 except that PS-1 was not used. The physical properties of the obtained film were measured, and the results are shown in Table 1.

Comparative Example 4

 Three layers (layer A / layer B / layer A) were prepared in the same manner as in Example 1 except that the extrusion amount and the take-up speed of the unstretched sheet were adjusted, the thickness of each layer was changed, and stretching and heat treatment were not performed. An unstretched film was made. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1.

Comparative Example 5

 A three-layer stretched film was prepared in the same manner as in Example 1 except that the two layers were composed of the A layer / B layer of SPS-1 / PS-1. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1.

Comparative Example 6

 Using the stretched film of FS-1 obtained in Comparative Example 1 and the stretched film of SPS-1 obtained in Comparative Example 2, an acrylic dry laminating adhesive, Ummebond BS—20 ◦ (Oshoku Kogyo Co., Ltd.) To form a laminated film of layer A / layer B / layer A. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1. The total haze of this film is high 13. / 6.

Comparative Example 7 SPS-3 and PET are co-extruded with a cast molding machine having a multilayer die (T-dye temperature: 300 ° C; take-off speed: lm / s), and cooled at the cold opening. SP S—3ZP ETZSF S_ A three-layer film of No. 3 was obtained. This film was stretched 3 × 3 times (at a temperature of 115 ° C.) at a table table to obtain a film. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1.

Comparative Example 8

 Instead of five? ? A film was prepared in the same manner as in Comparative Example 7 except that the T-die temperature was set to 320 ° C and the T-die temperature was set to 233 times (stretched to a temperature of 96 ° 0 to obtain a three-layer film).

 9

Got Lum. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1. The total haze of this film was high, 1'5%.

Comparative Example 9

The biaxially stretched film, the SFS-3 film, and the PC film were laminated with a curable urethane-based adhesive to obtain a three-layer film of SPS-3 / FC / SPS-3. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1.

Hereinafter, Examples 5 to 12 and Comparative Examples 10 to 12 will be described.

 The SPS, GPPS and additives used in Examples 5 to 12 and Comparative Examples 10 to 12 are as follows. '

 OS P S

PMS 1: syndiotactic polystyrene copolymer (manufactured by Idemitsu Petrochemical Co.) Comonomer: paramethylstyrene, copolymerization ratio 15 mol ⁰ / o, weight average molecular weight 2900,000

PMS 2: syndiotactic polystyrene copolymer (manufactured by Idemitsu Petrochemical Co., Ltd.) Comonomer: paramethylstyrene, copolymerization ratio: 12 mol ⁰ / o, weight average molecular weight: 230,000

PMS 3: syndiotactic polystyrene copolymer (manufactured by Idemitsu Petrochemical Co., Ltd.) Comonomer: paramethylstyrene, copolymerization ratio: 15 mol ⁰ / o, weight-average noon amount 200,000

 PMS 3: Syndiotactic polystyrene copolymer (manufactured by Idemitsu Petrochemical Co., Ltd.) Comonomer: paramethylstyrene, copolymerization ratio: 15 mol%, weight average molecular weight: 170,000.

 HOMO 1: Syndiotactic polystyrene (made by Idemitsu Petrochemical Co., Ltd.)

 Weight average molecular weight 3 0 0, 0 0 0

 HOMO 2: Syndiotactic polystyrene (made by Idemitsu Petrochemical Co., Ltd.)

 Weight average molecular weight 1 0 0, 0 0 0 '

 HOMO 3: Syndiotactic polystyrene (made by Idemitsu Petrochemical Co., Ltd.)

 Weight average molecular weight 4 0 0, 0 0 0

 OGPP S

GPP S 1: Atactic polystyrene (Dainippon Ink and Chemicals, trade name, U

 X 6 0), weight average molecular weight 4 4 0, 0 0 0

GPP S 2: atactic polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd., trade name: HH 3 2 ), Weight average molecular weight 3400,000

 GPP S3: atactic polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd., trade name: NF20)

 ), Weight average molecular weight 230,000

〇Additives (Master batch for adding antioxidant and anti-blocking agent)

 'For copolymer SFS, an anti-blocking agent aluminosilicate (Mitsuzawa Chemicals, Silton AMT 08) was mixed with 10 and OOO ppm powder in each PMS 1-4, and the mixture was mixed at 300 ° C. After melt extrusion, pelletized.

 • For Homo SPS, use the same amount of the same aluminosilicate as for the copolymer in each H〇M〇 1-4, and use the antioxidant pentaerythritol-tetrakis [3- (3,5-di-t-butyl-)] 4-Hydroxyphenyl) propionate] (trade name: I RGANOX 101, manufactured by Ciba-Shariti Tea Chemicals)

Example 5

 PMS 1 and GPP S 1 obtained by dry blending the master batch described above were extruded at 270 ° C with respective 50 mm single-screw extruders, and feed blocks were set at 270 ° C. It was co-extruded through a coat hanger die having a width of mm and cooled with a cooling port at 85 ° C. to obtain a 250 im multilayer unstretched sheet of SPS / GPP S / SPS. This unstretched sheet is continuously stretched 3.3 times at 105 ° C in the machine direction, then 3.8 times at 115 ° C in the transverse direction, and then stretched at 200 ° C. Heat treatment was performed for 10 seconds while relaxing in the width direction by 5% to obtain a three-layer stretched film of about 20 m.

Example 6

 A multilayer film was prepared in the same manner as in Example 5, except that PPS was replaced with PMS2 and GPPS was replaced with GPPS2. .

Example 7

 A multilayer film was prepared in the same manner as in Example 5, except that PMS was replaced by PMS3 and GPPS was replaced by GPPS3.

Example 8 HOMO 1 and GPF S 3 which were dry-blended one master batch were extruded at 300 ° C. and 270 ° C. with respective 5 Omm single screw extruders, and feed blocks set at 300 ° C. It was co-extruded through a coat hanger die having a width of 0 mm and cooled with a cooling roll at 85 ° C. to obtain a 200 multilayer unstretched sheet of SPS / GPPS / SPS. This unstretched sheet is continuously stretched 2.8 times in the longitudinal direction at 105 ° C, then stretched 3.3 times in the transverse direction at 115 ° C, and then stretched in width at 200 ° C. Heat treatment was performed for 10 seconds while relaxing 5% in the direction to obtain a three-layer stretched film of about 20 m.

Example 9

 A multilayer film was prepared in the same manner as in Example 5, except that PPS was replaced by PMS4 and GPPS was replaced by GFPS1.

Example 10

Except was extruded with PMS 1 2 and 0 wt _^0/0 dry blend GPP S layer to prepare a multilayer film in the same manner as in Example 5.

Example 1 1

Except was extruded GPP S 1 to the SPS layer 2 0 weight _^0/0 by dry blending to prepare a multilayer film in the same manner as in Example 5.

Example 1 2

 A multilayer film was prepared in the same manner as in Example 5, except that the discharge ratio of SPS and GFPS was changed as shown in Table 1.

Comparative Example 10

 A multilayer film was prepared in the same manner as in Example 8, except that HPS02 was used for SPS and GPPS1 was used for GFPS.

Comparative Example 1 1

 A multilayer film was prepared in the same manner as in Example 6, except that PPS was replaced by PMS2 and GPPS was replaced by GPPS3.

Comparative Example 1 2 A multilayer film was prepared in the same manner as in Example 7 except that SPS was changed to H0M03 and GFFS was changed to GPPS3.

 The material constituting the multilayer film, the film width effective rate, and the deflection temperature under load of the GPPS layer were measured by the following methods, and the results are shown in Table 2.

 • Effective film width

 Measure the amount of melt enthalpy by measuring the DSC at an arbitrary interval from the center of the film, and divide this by the amount of melt enthalpy of the SPS monolayer film to calculate the film layer ratio. That is, the SPS layer ratio is obtained by the following equation.

 S P S layer ratio = ΔΗπι (multi-layer film) / AHm (SP S single-layer film) [However, ΔΗιη indicates the amount of molten enthalpy. ]

Next, the fluctuation is 10 with respect to the average value of the SPS layer ratio in the width direction. The width within / ₀ is defined as valid and divided by the entire width of the film.

 If the layer ratio fluctuation exceeds 10%, uniformity of physical properties in the width direction cannot be maintained.

 -Deflection temperature under load of GPPS layer

The deflection temperature under load of the GPFS layer was measured in accordance with JISK 7207.

Table 2

 Hereinafter, Example 13 18 and Comparative Example 13 15 will be described.

The SP S GPFS used in Example 13 18 and Comparative Examples 13 to 15 and a method for producing the same are as follows. OS P s

 SPS31: Syndiotactic polystyrene (made by Idemitsu Petrochemical Co., Ltd.)

 Weight average molecular weight 2 2 0, 0 0 0

SPS32: Syndiotactic polystyrene copolymer (manufactured by Idemitsu Petrochemical Co., Ltd.) Comonomers: paramethylstyrene, copolymerization ratio: 12 mol ⁰ / o, weight average molecular weight: 230,000

 OGP P S

GPP S31: atactic polystyrene (made by Idemitsu Petrochemical Co., Ltd., trade name HH3

 2), weight average molecular weight 340,000

〇Additives (Master batch for adding antioxidants and antiblocking agents) • For SPS31, add an antiblocking agent aluminosilicate (Mizusawa Chemical, Shilton AMT08) to SPS31, 0, 0 0 0 pm, antioxidant pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-1-4-hydroxyphenyl) propionate] (Ciba-Sharititi Chemical Co., Ltd., trade name I RG ANOX 100 1) 0) was mixed with 3 Q, 00 ppm powder, melt-extruded at 30 Q ° C, and pelletized.

 • For SPS32, the same amount of aluminosilicate as that for SPS31 was mixed with SFS32 in the same amount of powder, and pelletized.

Example 13

SPS 3 1 / GPP S 3 1 / masterbatch 8 0/1 0/1 0 that were dry-blended at a ratio of weight% (SP S / GPP S ratio = 9 0/1 0 wt _^0/0) and GF PS Feed co-extruded 31 through a single 50 Omm single-screw extruder at 300 ° C through a 500 mm wide coat hanger die and cooled with a 85 ° C cooling roll As a result, a 250 wm multilayer unstretched sheet of SPS / GFP S / SPS was obtained. In this sheet, the layer ratio was set to 2/6/2 by setting the discharge ratio of each extruder. This unstretched sheet is continuously stretched 2.7 times at 105 ° C in the machine direction and then in the machine direction. After stretching 3.3 times at 15 ° C, the film was subjected to a heat treatment at 200 ° C for 10 seconds while relaxing 5% in the width direction to obtain a three-layer stretched film of about 20 m.

Example 14

 A three-layer stretched film having a layer ratio of 1/8/1 was manufactured using the same material and the same manufacturing method as in Example 13.

Example 15

 According to the same production method as in Example 13, a three-layer stretched film was produced by setting the surface material after dry blending to SPS / GPPS = 70/30.

Example 16

 According to the same production method as in Example 13, a three-layer stretched film was produced by setting the surface material after dry blending to SPS / GPFS = 50/50.

Example 17

Advance after the SPS 90 weight _^0/0 and GPPS 1 0 wt _^0/0 were dry blended, except that the melt-kneaded material in 300 ° C in a twin-screw press extruder and the intermediate layer, in the same manner as in Example 1 3 Thus, a three-layer stretched film was manufactured.

Example 18

SPS 32 / GPP S 3 1 / master one batch 80/1 0/1 0 wt ⁰ / o which were dry-blended at a ratio of (SPS / GPP S ratio = 90 Bruno 1 0 wt _^0/0) and GP PS 3 1 was extruded through a 50 mm (^ single screw extruder at 300 ° C feed block, 500 mm wide coat hanger die, co-extruded, cooled with 85 ° C cooling roll and A 250-layer unstretched sheet of / GPP S / SFS was obtained, and the sheet ratio was set to 2/6/2 by setting the discharge ratio of each extruder. The film is stretched 3.3 times in the longitudinal direction at 105 ° C, and then stretched 3.6 times in the transverse direction at 115 ° C. Heat treatment was performed for 2 seconds to obtain about 20 three-layer stretched films.

Comparative Example 1 3 SPS 3 1 / a masterbatch 90/1 0 wt _^0/0 5 what it was dry-blended at a ratio of Omm (^ feedblock set at 300 ° C in a single screw extruder, through a coat hanger die of 500 mm width And extruded and cooled by a cooling roll at 85 ° C. to obtain a single-layer unstretched sheet of 250 m. This unstretched sheet was continuously stretched 2.7 times at 105 ° C. in the longitudinal direction. Then, the film was stretched 3.3 times at I 15 ° C in the transverse direction, and then heat-treated at 200 ° C for 10 seconds while relaxing 5% in the width direction to obtain a single-layer stretched film of about 20 m.

Comparative Example 1 4

SPS31 / mass batch dry blended at 90/10 weight ⁰ / o and GPP S31 50mm each (^ Feed block set to 300 t with single screw extruder, 500 It was extruded through a coat hanger die with a width of mm and cooled with a cooling roll at 85 ° C to obtain a 250 m multilayer unstretched sheet of SP SZGPP S / SPS. The unstretched sheet was continuously stretched 2.7 times at 105 ° C in the machine direction and then 3.3 at 115 ° C in the transverse direction. After stretching twice, while relaxing 5% in the width direction at 200 ° C

Heat treatment was performed for 10 seconds to obtain a three-layer stretched film of about 20 m.

Comparative Example 15

SPS 3 1 / GPPS 3 1 / masterbatch 1 0/80/1 0 which were dry-blended at a ratio of weight% (SPS / GPPS ratio = 20/80 weight _^0/0) and GF PS 3 of 1, respectively 50 mm Single-screw extruder feed co-extruder set at 300 ° C, co-extrusion through 500 mm wide coat hanger die, cool at 85 ° C cooling port, SPS / GPP S / SPS 250 m A multilayer unstretched sheet was obtained. In this sheet, the layer ratio was set to 2/6/2 by setting the discharge ratio of each extruder. This unstretched sheet is continuously stretched 2.7 times at 105 ° C in the machine direction and then 3.3 times at 115 ° C in the transverse direction. A 20 m three-layer stretched film was obtained. The films obtained in the above Examples and Comparative Examples were subjected to an adhesion test by the following method, and the results are shown in Table 3. Dry laminating agent Dick Dry LX 90 1 (base agent) / KW75 (curing agent) was diluted with methyl ethyl ketone so that the non-volatile content concentration became 10%, and the resulting adhesive solution was used in the above Example. A film having a thickness of 10 m was formed on the film prepared in Comparative Example using a hand coater, and dried at 150 ° C. for 5 minutes using a vacuum drier. The same SPS film was heat-sealed on the film on which the adhesive layer was formed at 150 ° C, 2 kg / cm ² , and 2 seconds using a heat seal tester, and then heated to 40 ° (: 24 hours). It was paged.

Heat seal peel strength

 Using a tensile tester, each film was held on a chuck, and the strength when pulled at a speed of 200 mm / min was measured.

 Table 3

Hereinafter, Examples 19 to 29 and Comparative Examples 16 to 19 will be described ₍ The SFS, GPPS and additives used in Examples 19 to 29 and Comparative Examples 16 to 19 are as follows. The weight average molecular weight was measured by gel permeation chromatography (GPC) in trichlorobenzene at 145 ° C.

 The physical properties of the films produced in Examples 19 to 29 and Comparative Examples 16 to 19 described below were measured in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 9.

OS P S

SPS41: Syndiotactic (styrene-p-methylstyrene) copolymer

(Manufactured by Idemitsu Petrochemical Co., Ltd.), p-methyl styrene, 1 2 mole _^0/0, a weight average molecular weight 230, 000

 S P S 42: Syndiotactic (styrene-p-methylstyrene) copolymer

(Manufactured by Idemitsu Petrochemical Co., Ltd.), p-methyl styrene, 7 mole _^0/0, a weight average molecular weight 290, 000

 SPS 43: Syndiotactic (styrene-p-methylstyrene) copolymer

(Manufactured by Idemitsu Petrochemical Co., Ltd.), p-methyl styrene, 1 5 mole _^0/0, a weight average molecular weight of 70, 000

 SP44: Syndiotactic styrene homopolymer (made by Idemitsu Petrochemical Co., Ltd.), weight average molecular weight 220,000

 SPS 45: Syndiotactic styrene homopolymer (made by Idemitsu Petrochemical Co., Ltd.), weight average molecular weight 3 Q 0,000

 OGPP S

 • PS1: atactic polystyrene (trade name: HH32, manufactured by Idemitsu Petrochemical Co., Ltd.), weight average molecular weight 340,000

 P S 2: Atactic polystyrene (Dainippon Ink & Chemicals, product name, UX

 60 0). Weight average molecular weight 440,000

PS 3: atactic polystyrene (made by Idemitsu Petrochemical Co., trade name HH30), Weight average molecular weight 270,000

 〇Additives

 • Anti-blocking agent: Aluminosilicate (Mitsuzawa Chemicals, Shilton AMT08)

 'Antioxidant: Penyu erythrityl-tetrakis [3- (3,5-di-t-butyl 4-hydroxyphenyl) probionate] (Ciba-Sharititi Chemical Co., Ltd., trade name I RGANOX 1 0 1 0)

Production Example 3 (Preparation of one batch of additive master)

 1000 ppm of an antiblocking agent and 2000 000 pm of an antioxidant were mixed with SPS41, and the mixture was melt-extruded at 280 ° C to obtain pellets.

Production Example 4 (Preparation of kneading material for layer B)

PS 1 (80 wt _^0/0) and SP S 4 1 (20 wt _^0/0) were mixed, after solvent extrusion melt at 2 80 ° C, and the pellet.

Example 19

SP S 4 1 (90 wt _^0/0) and the additives mixed compound masterbatch (1 0 wt _^0/0) and PS 1 (80 wt%) and SPS 4 1 (20 weight _^0/0) The mixture was extruded at 300 ° C (5 ° πιπιΦ single screw extruder at 300 ° C, respectively, at 280 ° C, and extruded through a feed block set at 280 ° C and a coat hanger die, It was cooled by a cooling roll at 85 ° C to obtain a three-layer unstretched sheet of layer A / layer B / layer A. The unstretched three-layer sheet was continuously stretched in a longitudinal direction at 103 ° C at 3. The film was stretched 0 times, then stretched 3.6 times at i 15 ° C in the horizontal direction, and then heat-treated at 200 ° C. for 4 seconds while relaxing 10% in the width direction. The physical properties of the stretched film were measured, and the results are shown in Table 4.

Example 10

Instead of PS 1 (80 wt ⁰ / o) and SPS 4 mixture of I (20 weight _^0/0), except for using a kneading material prepared in Preparation Example 2, the same operation as in Example 1 9, 3-layer stretcher Table 4 shows the physical properties of the manufactured ilum.

Example 2 1

Instead of PS 1 (8 0 wt _^0/0) and SPS 4 1 (2 0 weight _^0/0) a mixture of, the end of the film obtained in PS 1 (5 0 wt _^0/0) of Example 1 9 A three-layer stretched film was produced in the same manner as in Example 19, except that the mixed material (50% by weight) was used, and the physical properties are shown in Table 4.

Example 22

Instead of PS 1 mixture of (8 0% by weight) and S 5P S 4 1 (2 0 weight _^0/0), use a mixture of PS 1 (9 0 wt%) and SPS 4 1 (1 0%) The same procedure as in Example 19 was carried out, except that the three-layer stretched film was produced, and the physical properties are shown in Table 4. Example 2 3

Instead of PS 1 (8 0 wt _^0/0) and SPS 4 1 mixture of (2 0 weight ⁰ / o), use a mixture of PS 1 (8 0% by weight) and SPS 4 3 (2 0 wt%) The same procedure as in Example 19 was carried out, except that the three-layer stretched film was produced, and the physical properties are shown in Table 4. Examples 24 and 25

 In Example 19, the extrusion amount of each extruder was changed, and films having different layer ratios and thicknesses were prepared. The physical properties are shown in Table 4.

Example 26

 A three-layer stretched film was produced in the same manner as in Example 19, except that SPS42 and PS2 were used in place of SPS4KPS1, respectively, to produce a three-layer stretched film.

 A three-layer stretched film was manufactured in the same manner as in Example 19 except that SPS44 was used instead of SPS41, and the physical properties thereof are shown in Table 4.

Example 2 7

Except that SPS 45 and PS 2 were used instead of SPS 41 and PS '1, respectively. By operating in the same manner as in Example 19, a three-layer stretched film was produced, and its physical properties are shown in Table 4.

 A three-layer stretched film was produced in the same manner as in Example 19 except that PS 3 was used instead of PS 1, and the physical properties are shown in Table 4.

Comparative Example 16

Instead of PS 1 mixture of (8 0 wt ^0/6) and SPS 4 1 (2 0 weight _^0/0), except for using the FS 1 (1 0 0 wt _^0/0), Example 1 9 The same operation was performed to produce a three-layer stretched film, and its physical properties are shown in Table 4.

Comparative Example 1 7

 A single layer stretched atactic polystyrene film was prepared using only PS1, and the physical properties are shown in Table 4.

Comparative Example 1 8

SPS 4 1 (9 0 wt _^0/0) a mixture using only the master one batch prepared in Preparation Example 3 (1 0 wt _^0/0), create a syndiotactic polystyrene monolayer stretched film, physical properties Are shown in Table 4.

Comparative Example 1 9

SPS 4 1 (9 0 wt _^0/0) and a mixture and FS 1 master one batch prepared in Preparation Example 3 (1 0 wt _^0/0), and adjust the take-up speed of the undrawn sheet one Bok, A-layer No. B-layer / A-layer three-layer unstretched film was prepared, and its physical properties are shown in Table 4.

Actual Actual Actual Actual Actual Actual Actual Actual Actual Actual Ratio Ratio Ratio Table 4

 施 施 較 較

 Ii Ii ^ ^ ^ Italy

 2222222222-_.-----111114878 9 ο67969352-_ 1

 4 (continued)

 Manufacturing method SPS layer crystal

 Degree (%) Haze

GPPS + SPS pellet plain 4 7

 Co-extrusion, co-stretching, heat treatment

 GPPS + SPS melt kneading, 4 6

 Co-extrusion, co-stretching, ^ processing

 GPPS + Multilayer film scrap material blend, 4 7

 Melt kneading, coextrusion, codrawing, heat treatment

4 7 2 Example 19 and 4 7 3 Example 19 and 4 7 3 Example 19 and 4 7 9 Example 19 and 4 7 7 Example 19 and 4 7 3 Example 1 9 5 1 4 Example 1 9 and 5 3 6 Example 1 9 4 5 4 Coextrusion, coextension, heat treatment 4 7 2 Extrusion, stretching 1 extrusion, stretching, heat treatment 4 9 8 Coextrusion 5 9 4 (continued)

 Hereinafter, Examples 30 to 37 and Comparative Examples 20 to 23 will be described.

 The SPS, GPPS and additives used in Examples 30 to 37 and Comparative Examples 20 to 23 are as follows.

 OS P S

SPS 5 1: syndiotactic polystyrene copolymer (manufactured by Idemitsu Petrochemical Co., Ltd.) comonomer one para-methyl styrene, copolymerization ratio 1 2 mole ^_0/0,

 M I = 8, melting point 242 ° C

 Weight average molecular weight 230,000

 SPS 52: Syndiotactic polystyrene polymer (made by Idemitsu Petrochemical Co., Ltd.)

 M I = 9, melting point 270 ° C

 Weight average molecular weight 220,000

 OGPP S

GPPS 51: Atactic polystyrene (made by Idemitsu Petrochemical Co., trade name: HH3

2), weight average molecular weight 340,000 Styrene-gene or styrene-olefin block copolymers or graft copolymers

 P S C 1: S B S (made by Asahi Kasei Corporation, trade name: Asahi Flex 8 10)

 Styrene content 70 mol% or more

 PSC 2: SB S (Asahi Flex 8330, manufactured by Asahi Kasei Corporation)

 Styrene content 70% mol or more

 P SC 3: S EF S (manufactured by Kuraray, trade name: Septon 2 104)

 Styrene content 65 mol%

 PSC 4: SEBS (made by Kuraray, trade name: Septon 8104)

 Styrene content 60 mol%

 P SC 5: S EB S (made by Kuraray, trade name: Septon 8006)

 Styrene content 30 mol%

 〇Additives (Masterbatch for adding antioxidants and antiblocking agents)

 'For copolymers, anti-blocking agent aluminum silicate (Shilton AMT08, manufactured by Mizusawa Idani, Ltd.) was mixed with SFS51 and powdered at 100, OOO ppm and melted at 300 ° C. After extruding, the pellets were toyed.

 For Homo SPS, use the same amount of aluminosilicate as that for the above copolymer in SP S52, and add the antioxidant pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-1-) Hydroxyphenyl) propionate] (Cibas Specialty Chemicals Co., Ltd., trade name: IRGANOX 10100) was mixed with 100,000 ppm powder, melt-extruded, and pelletized.

 • Intermediate layer For GPP S, GFP S51 is mixed with antioxidant I RGANOX 11010 and Sumilizer-I-GS (manufactured by Sumitomo Chemical Co., Ltd.) in powders of 10, 00 Oppm, respectively. I did it.

 Example 30

SPS 51 / master batch = 90/10% by weight dry blended Those fine GPP S 5 1 / F SC 1 / master one batch 7 2/2 0/8 wt _^0/0 Drive trend at each 5 Omm (^ single-screw extruder at 2 7 0 ° C Extrusion Feed block set at 270 ° C, co-extrusion through a coat hanger die with a width of 500 mm, cooled with a chill roll at 85 ° C, and cooled to 250 p.p. for SPS / GPP S / SPS. m A multilayer unstretched sheet was obtained, and the layer ratio was set to SFS / GPP S / SPS: 2/6/2 by setting the discharge ratio of each extruder. Stretched 3.3 times at 105 ° C in the direction, then stretched 3.8 times at 115 ° C in the transverse direction, and relaxed 1 Oo / o in the width direction at 120 ° C. Then, a heat treatment was performed for 10 seconds to obtain about 20 three-layer stretched films.

Example 3 1

 A three-layer stretched film was obtained in the same manner as in Example 30, except that the blend ratio of PSC 1 constituting the intermediate layer was changed to 10% by weight.

Example 3 2

 A three-layer stretched film was obtained in the same manner as in Example 30, except that the layer ratio was changed to SPS / GPPS / SPS = 1/8 / l.

Example 3 3

 A three-layer stretched film was obtained in the same manner as in Example 30 except that PSC2 was used instead of PSC1 blended in the intermediate layer.

Example 3 4

SPS 5 2 / mass evening drive in one batch = 9 0/1 0 wt%及beauty GPP S 5 1 / P SC 3 / master one batch 7 2/2 0/8 wt _^0/0 which were dry blended with Lend The extruded product was extruded at 290 ° C and 270 ° C with each 50 mm single screw extruder, and co-extruded through a feed block set at 290 ° C and a coat hanger die of 50 Omm width, It was cooled by a cooling roll at 85 ° C. to obtain a 250 m multilayer unstretched sheet of SPS / GPP S / SPS. For this sheet, the layer ratio was set to 3/3 / 0-? 3 / ^? 3: 2/6/2 according to the setting of the discharge ratio of each extruder. This unstretched sheet The film is stretched continuously 2.8 times at 105 ° C in the longitudinal direction, then stretched 3.2 times at 115 ° C in the horizontal direction, and then relaxed 12% in the width direction at 120 ° C. Then, heat treatment was performed for 10 seconds to obtain a three-layer stretched film of about 20 m.

Example 35

 A three-layer stretched film was obtained in the same manner as in Example 34, except that SPS 52 was used instead of SPS 51 and PSC 4 was used instead of PSC 3 blended in the intermediate layer.

Example 36

 The surface material is dry blended with SPS 5 1 / PSC 1 / master batch = 8 1/10/9% by weight, and the intermediate layer is GPPS 51 / PSC 1 / master batch = 72/20/8 weight %, To obtain about 20 three-layer stretched films in the same manner as in Example 30.

Example 37

The surface layer material in SPS 5 1 / FSC 1 / master one batch = 8 1/1 0/9 weight _^0/0 and those dry blended and the intermediate layer and the GPP S 5 1 / masterbatch = 90/10 wt% Except for the above, a three-layer stretched film of about 20 m was obtained in the same manner as in Example 30.

Comparative Example 20.

And those dry blended surface layer material with SPS 5 1 / master one batch = 90/1 0 wt%, except that the intermediate layer and GPPS 5 1 / masterbatch = 90/1 0 wt _^0/0 'Example In the same manner as in Example 30, a three-layer stretched film of about 20 m was obtained. Comparative Example 2 1

Except that the intermediate layer and dry blend of GPPS 5 1 / PSC 1 / master one batch = 36/60/4 wt _^0/0, to obtain a 3-layer stretch off Ilm to about 20 m in the same manner as in Example 30 .

Comparative Example 22. Except that the surface layer was used as a dry blend of GPPS 5 1 / P SC 1 / masterbatch = 4 0.5 / 5 5 / 4.5 by weight _^0/0, 3 to about 20 m in the same manner as in Example 3 0 A layer stretched film was obtained.

Comparative Example 2 3

The surface layer material in SPS 5 1 / master one batch = 90/1 0 wt _^0/0 and those dry blended, and the intermediate layer GPP S 5 1 / PSC 5 / master one batch = 7 2/20/8 wt% Except having performed, a three-layer stretched film of about 20 m was obtained in the same manner as in Example 30.

 With respect to the films produced in the above Examples and Comparative Examples, the film impact bow strength and haze were measured by the following methods. Table 5 shows the results.

 • Evaluation of film impact strength

 The film was punched out from below with a pendulum having a head diameter of 1 inch and measured using an impact tester (pendulum type) manufactured by Toyo Seiki Seisaku-sho.

 -Haze rating

 The measurement was performed according to JIS K7105.

 Table 5

 Middle class

Example 30 SPS51 GPPS51 / PSC1 80 / 20wt% 2/6/2 Example 31 SPS51 GPPS51 / PSC1 90 / 10wt% 2/6/2 Example 32 SPS51 GPPS51 / PSC1 80 / 20wt ° / o 1/8/1 Example 33 SPS51 GPPS51 / PSC2 80 / 20wt% 2/6/2 Example 34 SPS52 GPPS51 / PSC3 80 / 20wt% 2/6/2 Example 35 QPS52 GPPS51 / PSC4 90 / 10wt ° / o 2/6/2 Example 36 SPS51 / PSC1: 90/10 t% GPPS51 / PSC1 80/20 t% 2/6/2 Example 37 SPS51 / PSC1: 90/10 wt% GPPS51 2/6/2 Comparative Example 20 SPS51 GPPS51 2/6 / 2 Comparative Example 21 ςρ351 GPPS51 / PSC1 40/60 t% 2/6/2 Comparative Example 22 SPS51 / PSC1: 45 / 55wt ° / o GPPS51 2/6/2 Comparative Example 23 SPS51 GPPS51 / PSC5: 80 / 20wt% 2/6/2 Table 5 (continued)

 Hereinafter, Example 3842 and Comparative Example 2425 will be described.

 The SPS, GPPS and additives used in Example 3 842 and Comparative Example 24 25 are as follows.

 OS P S: Syndiotactic polystyrene copolymer (made by Idemitsu Petrochemical Co., Ltd.) Comonomer: paramethylstyrene, copolymerization ratio: 12 mol%

 Weight average molecular weight 230,000

 OGPP S: Acoustic polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd., trade name: HH30) Weight average molecular weight: 270,000.

 〇Antioxidant

 AO 1: Sumi 1 iz er GS manufactured by Sumitomo Chemical Co., Ltd.

(5% weight loss temperature under N ₂ 270 ° C),

 AO 2: Ciba-Sharititi Chemical Co., Ltd. I RGANOX 10 0

(5 Q / Q weight loss temperature under N ₂ 3 3 5 ° C)

 AO 3: PEP 36 manufactured by Adeka Gas Chemical Co., Ltd.

(N 5% weight loss temperature 3 3 2 ° C in ₂ below) AO 4: Chivas Specialty Chemicals I RGANOX 1 2 2 2 (5% weight loss temperature under N ₂ 2 1 3 ° C)

Example 3 8

A0 1 to 0.1 mixture 1 weight _^0/0 powder to GPP S and after melt-extrusion at 3 0 0 ° C, and Perez Bokui匕.

 The resulting GFP S pellets and SPS were extruded at 270 ° C with their respective 5 Omm single screw extruders, a feed block set at 270 ° C, and a 500 mm wide coat hanger die. Extruded through a cooling roll at 85 ° C to form a 250 m multilayer unstretched sheet of SP.S / GPF SZS PS continuously for 8 hours. The washings were collected, evaporated to dryness by an evaporator, weighed, and the results are shown in Table 6.

Example 3 9.

 The operation was performed in the same manner as in Example 38, except that AO 2 was used as the antioxidant. The weight of the residue after evaporating the roll washing liquid to dryness was measured, and the results are shown in Table 6.

Example 40

 The operation was performed in the same manner as in Example 38, except that AO 3 was used as the antioxidant. The weight of the residue after evaporating and drying the roll washing solution was measured, and the results are shown in Table 6.

Example 4 The same operation as in Example 38 was carried out except that 0.1% by weight of each of AO 1 and A02 was added as an antioxidant, and the weight of the residue after evaporating the roll washing liquid to dryness was reduced. The measurement was performed and the results are shown in Table 6.

Example 4 2

 The same operation as in Example 38 was carried out except that 0.1% by weight of AO 2 and AO 3 were added as antioxidants, respectively. Is shown in Table 6.

Comparative Example 2 4 The operation was performed in the same manner as in Example 38, except that no antioxidant was added to GP PS. The weight of the residue after evaporating and drying the roll washing liquid was measured, and the results are shown in Table 6.

Comparative Example 5

 The operation was performed in the same manner as in Example 38, except that AO 4 was used as the antioxidant. The weight of the residue obtained after evaporating and drying the mouthwash solution was measured, and the results are shown in Table 6.

 Table 6

 ■ Hereinafter, Examples 43 to 48 and Comparative Examples 26 to 29 will be described.

 The SPS, GPPS and additives used in Examples 43 to 48 and Comparative Examples 26 to 29 are as follows.

OS P S

SPS71: Syndiotactic polystyrene copolymer (manufactured by Idemitsu Petrochemical Co.) Comonomer: paramethylstyrene, copolymerization ratio: 12 mol%, weight average molecular weight: 230,000

 SPS72: Syndiotactic polystyrene polymer (made by Idemitsu Petrochemical Co., Ltd.) Weight average molecular weight 220,000

 OGP P S

GP P S 71: atactic polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd., trade name: HH 3

2), weight average molecular weight 340,000 〇Additives (Master batch for adding antioxidant and anti-blocking agent)

 • For copolymers, SPS71 is mixed with an aluminosilicate anti-available agent (Shilton AMT08, manufactured by Mizusawa Chemical Co., Ltd.) at 10 ppm and OOO ppm powder, and melt-extruded at 300 ° C. , Pelletized.

 〇 For Homo SPS, use the same amount of aluminosilicate as for the above copolymer in SP S72, and add the antioxidant pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxy) [Phenyl) propionate] (Cibas-Sharititi, manufactured by Chemical Co., Ltd., trade name: IRGANOX 10100) was mixed with 100,000 ppm powder, melt-extruded, and pelletized.

 〇Intermediate layer For GPP S, GPP S71 is mixed with antioxidant I RGANOX 11010 and Sumilizer-I-GS (manufactured by Sumitomo Chemical Co., Ltd.) in powders of 10, 00 Oppm, respectively. I did it.

Example 4 3

 SPS71 and GPP S71, which were dry-blended master batches, were extruded at 50 ° C single screw extruder at 270 ° C, feedblock set at 70 ° C, It was co-extruded through a coat hanger die having a width of 0 mm and cooled with a cooling port at 85 ° C to obtain a 250 wm multilayer unstretched sheet of SPS / GPP S / SPS. In this sheet, the layer ratio was set to SPS / GPP SZS Ps: 2/6/2 by setting the discharge ratio of each extruder. This unstretched sheet is continuously stretched 3.3 times at 105 ° C in the machine direction and then 3.8 times at 115 ° C in the transverse direction. Heat treatment was performed for 10 seconds while relaxing in the direction by 10% to obtain about 10 three-layer stretched films. , '

Example 4 4

 A three-layer stretched film was obtained in the same manner as in Example 43 except that the heat treatment temperature was set at 140 ° C.

Example 4 5 A three-layer stretched film was obtained in the same manner as in Example 43 except that the heat treatment temperature was changed to 160 ° C.

Example 4 6

A three-layer stretched film was obtained in the same manner as in Example 45, except that the intermediate layer was composed of a dry blend of SPS71 / GPPS71: 20/80 weight ⁰ / o.

Example 4 7

 A three-layer stretched film having a layer ratio of 1/8/1 was obtained in the same manner as in Example 45. Example 4 8

 A three-layer stretched film was obtained in the same manner as in Example 45, except that the SPS layer was composed of SPS72.

Comparative Example 2 6

 A three-layer stretched film was obtained in the same manner as in Example 43, except that the heat treatment temperature was set at 200 ° C.

Comparative Example 1 7

A three-layer stretched film was obtained in the same manner as in Comparative Example 26, except that the intermediate layer was composed of a dry blend of SPS71 / GPPS71: 80/20 weight ⁰ / o.

Comparative Example 2 8

 A three-layer stretched film was obtained in the same manner as in Comparative Example 26, except that SPS was changed to SPS72 and the heat treatment temperature was set to 220 ° C.

Comparative Example 2 9

Dry blending of SP S71 and GPP S71 dry-blended from one master batch at 20/80% by weight, extruded with a 50 mm single screw extruder at 2701 and set at 270 ° C The feed block was extruded through a coat hanger die having a width of 500 mm, and cooled with a cooling roll at 85 ° C. to obtain a 250-layer single-layer unstretched sheet. This unstretched sheet is continuously stretched 2.7 times at 105 ° C in the longitudinal direction, and then stretched 3.0 times at 115 ° C in the transverse direction. 1 10% while relaxing in the width direction by 10% Heat treatment was performed for 2 seconds to obtain a stretched film of about 20 wm.

 The film impact strength of the films produced in the above Examples and Comparative Examples was measured by the following method. Table 7 shows the results.

 Evaluation of film impact bow angle

 The film was punched from below with a pendulum with a 1-inch diameter, and measured with a 1-inch impact head using a Toyo Seiki Seisakusho film impact tester (pendulum type).

• Table 7

Industrial applicability

 The laminated film of the present invention is excellent in heat resistance, oil resistance, and mechanical strength, and is also excellent in both heat heat suitability (thermoformability) and transparency.

The weight average molecule of the styrenic polymer having a syndiotactic structure of the layer A according to the present invention. (SP SMw) and the weight-average molecular weight (GPP SMw) of the styrene polymer having an atactic structure in the B layer, and the range of (SP SMw / GPP SMw) is limited in the width direction. It is a polystyrene-based multi-layer film with good appearance and good quality without unevenness of layer ratio distribution, interface roughness, etc., in the present invention, wherein the A layer has a syndiotactic structure. the polymer, § evening Kuchikku 2-5 0 weight styrene polymer structure _^0/0 added with a composition volume polystyrene-based product, the layer film, adhesion of the lamination of the printing property and other substrates Excellent secondary workability, etc., and good layer ratio distribution, the mechanical properties are uniform in the width direction, and there is no interface roughness and the appearance is good.

 The blend of the styrene-based polymer having an atactic structure in the B layer of 50 to 95% by weight and the styrene-based polymer of syndiotactic polyethylene or the polymer composition containing the blend according to the present invention. Polystyrene-based laminated film at 0% by weight is inexpensive, has excellent transparency, heat resistance, oil resistance, thermoformability, etc., and has improved toughness.

At least one of the A layer and the B layer according to the present invention contains 2 to 50 of a styrene-gen or styrene-olefin block or graft copolymer having a styrene content of 50 mol ⁰ / o or more. The heat-resistant, chemical-resistant, rigid, easy-to-cut, dead-fold, moisture-resistant, mold-releasing, thermoforming, and heat-sealing adhesion properties of the polystyrene-based laminated film according to claim 1 containing by weight. In addition to being excellent in various film properties such as, for example, it has high transparency, remarkably improved toughness, and can be manufactured efficiently at low cost.

5% weight loss temperature between the syndiotactic styrene polymer or the polymer composition containing the polymer and the atactic styrene polymer or the polymer composition containing the polymer according to the present invention. There 2 4 0 ° C over 0.0 of an antioxidant 0 1 -0. 5 wt _^0/0 by using a styrene-based material added, 2 5 0~ 3 0 0 ° C in melt co According to the method for producing a polystyrene-based laminated film to be extruded, a laminate having good moldability and good appearance without any fouling, fumes, eyes, foaming, etc. on a roll due to thermal decomposition of the GFPS layer during extrusion can be efficiently produced. It can be manufactured well, can greatly improve continuous productivity, and can provide useful laminated sheets and films for various uses.

 A syndiotactic styrenic polymer having a molecular weight of 150,000 to 300,000 or a composition (A) containing this polymer; A styrene polymer having an atactic structure of 0000 or more or a composition (B) containing this polymer is melt-coextruded at 250 to 300 ° C. Polystyrene-based laminated films manufactured by heat treatment at a temperature of 0 ° C or less have heat resistance, chemical resistance, rigidity, transparency, easy cutting, dead hold, moisture resistance, mold release, and heat resistance. A styrene resin laminate excellent in moldability, heat seal adhesion, and other various film properties, and particularly excellent in toughness, can be efficiently produced and can be provided at a low cost.

 Therefore, the polystyrene-based laminated film of the present invention can be used for various films, bags, and containers for industrial use such as food, medicine, stationery, daily use packaging films and containers, release films, adhesive tapes, capacitors, and dielectrics. Useful as

Claims

The scope of the claims

1. A laminated film in which the following layer A is laminated on both sides of layer B, wherein the total haze of the laminated film is 10% or less.

 A layer: A layer composed of a styrene polymer having a syndiotactic structure or a resin composition containing the same, wherein the styrene polymer has a crystallinity of 20% or more.

 Layer B: a layer made of a styrenic polymer having an atactic structure or a resin composition containing the same.

 2. The polystyrene-based laminated film according to claim 1, wherein the ratio of the thickness of each layer of the A layer / B layer ZA layer is 118 / 1-2 to 1/2/2.

 3. The polystyrene-based laminated film according to claim 1, wherein no adhesive is present between any of the A layer and the B layer.

 4. The layer A has a weight average molecular weight of 150,000 to 300,000, the layer B has a weight average molecular weight of 220,000 or more, The ratio (SPSMw / GP PSMw) of the weight average molecular weight (SP SMw) of the styrene polymer having an atactic structure to the weight average molecular weight (GPP SMw) of the styrene polymer having an atactic structure in the B layer is 0.3 to 0. 2. The polystyrene-based laminated film according to claim 1, which is 9.

 5. The polystyrene-based laminated film according to claim 1, wherein the deflection temperature under load of the layer B is 80 ° C or more.

 6. The polystyrene-based laminated film according to claim 1, wherein the A layer is a composition obtained by adding 2 to 50% by weight of a styrene-based polymer having an atactic structure to a styrene-based polymer having a syndiotactic structure.

7. The layer B is composed of a composition obtained by adding a styrene polymer having a syndiotactic structure to a styrene polymer having an atactic structure in an amount of 50% by weight or less, 2. The polystyrene-based laminated film according to claim 1, wherein the ratio of the weight-average molecular weight of the styrene-based polymer having an atactic structure / the weight-average molecular weight of the styrene-based polymer having an atactic structure is 0.3 to 0.9.

8. B layer Purendo of styrene polymers of styrene polymer 5 0-9 5 weight _^0/0 and Shinjio tactic structures Atakuchikku structure or polymer composition containing the Purendo was 5 - 5 0 wt ⁰ 2. The polystyrene-based laminated film according to claim 1, wherein the ratio is / ₀ .

 9. The polystyrene-based laminated film according to claim 8, wherein the molecular weight of the syndiotactic styrene-based polymer used for the layer B is not more than the molecular weight of the styrene-based polymer having an atactic structure.

1 0. A layer and 2-5 0 weight at least one layer having a styrene content of between 5 0 mol% or more of styrene one diene-based or styrene one year old olefin-based Purodzuku or graph preparative copolymer of layer B ⁰ / The polystyrene-based laminated film according to claim 1, which includes o.

1 1. 2 9 0 ° C of the polymer or the resin composition becomes polymer or resin composition and the layer B becomes A layer. Shear rate 1 0- 'sec-melt viscosity ratio at ¹ 0.3 to 3 The method for producing a polystyrene-based laminated film according to claim 1, wherein the polymer or the composition is subjected to melt coextrusion and then stretched.

 1 2. The layer A has a weight average molecular weight of 150,000 to 300,000, the layer B has a weight average molecular weight of 220,000 or more, The ratio (SP SMw / GPP SMw) of the weight average molecular weight (SP SMw) of the syndiotactic styrenic polymer to the weight average molecular weight (GPF SMw) of the atactic styrenic polymer in the B layer is 0. 5. The method for producing a polystyrene-based laminated film according to claim 4, wherein the styrene-based material of 3 to 0.9 is melted at 250 to 300 ° C. and co-extruded.

13. The method for producing a polystyrene-based laminated film according to claim 12, wherein the co-extrusion is followed by cooling and biaxial stretching.

14. A composition comprising 2 to 50% by weight of a tactic styrenic polymer added to a syndiotactic styrenic polymer, a tactic styrenic polymer, and optionally a syndiotactic styrenic polymer. 7. The method for producing a polystyrene-based laminated film according to claim 6, wherein the composition comprising the styrene-based polymer is melt-coextruded, cooled, and biaxially stretched.

15. A styrene-based polymer having a crystallinity of 20% or more having a syndiotactic structure or a polymer composition containing this polymer, and a styrene-based polymer having an atactic structure having a weight of ^{0 to} 95% 0/6 and 9. The polystyrene-based laminated film according to claim 8, which is stretched after melt co-extrusion using a blend of a styrene polymer having a syndiotactic structure or a polymer composition containing the blend in an amount of 5 to 50% by weight. Production method.

 16. The method for producing a polystyrene-based laminated film according to claim 15, wherein the molecular weight of the styrene-based polymer having a syndiotactic structure is not more than the molecular weight of the styrene-based polymer having an atactic structure.

17. A syndiotactic styrene-based polymer or a composition containing this polymer and an atactic styrene-based polymer or a composition containing this polymer are used. styrene content at least one is used to include 5 0 mole ^0/6 more styrene one diene-based or styrene one year old olefin-based proc or graft copolymer of 2-5 0% by weight, melt-coextrusion of these 10. The method for producing a polystyrene-based laminated film according to claim 10, wherein the film is cooled and stretched.

18. The 5% weight loss temperature of the syndiotactic styrene polymer or the polymer composition containing this polymer, and the atactic styrene polymer or the polymer composition containing this polymer is 5%. Antioxidant above 240 ° C

A method for producing a polystyrene-based laminated film that is melt-coextruded at 250 to 300 ° C. using a 5% by weight added styrene-based material.

1 9. Styrene-based polymer having atactic structure or polymer group containing this polymer Styrene with a syndiotactic structure is added to both sides of a layer of a styrene-based material in which an antioxidant with a 5% weight loss temperature of 140 ° C or higher is added to the product. The polystyrene according to claim 18, wherein the polystyrene has a three-layer structure in which layers composed of a system polymer or a polymer composition containing the polymer are laminated, and the layer ratio is 1/1/8/1 to 2/1/2. A method for producing a len-based laminated film.

 20. The method for producing a polystyrene-based laminated film according to claim 18 or 19, wherein the co-extrusion is followed by cooling and biaxial stretching.

 2 1. A styrene polymer having a syndiotactic structure with a molecular weight of 150,000-300,000 or a composition (A) containing this polymer, and a molecular weight of 220,000 , A styrene-based polymer having an atactic structure of at least 0.000 or a composition (B) containing this polymer, at 250 to 300 ° C by melt co-extrusion. A method for producing a polystyrene-based laminated film that is heat-treated at a temperature of C or lower.

2 2. The composition as (A), claim to use those obtained by adding in a proportion of syndiotactic 2-5 0 weight styrene polymer of § evening Kuchikku structure styrenic polymer structure _^0/0 2 2. The method for producing a polystyrene-based laminated film according to 1.

As 2 3. composition (B), in claim 2 1 that use plus a proportion of the styrene-based polymer Shinjiota 5 styrenic polymer Kuchikku structure 5 0 wt _^0/0 Atakuchikku structure The method for producing a polystyrene-based laminated film according to the above.

G 1