TW570873B - Polypropylene multilayered film - Google Patents

Abstract

The purpose of the present invention is to provide a non-chlorine type polypropylene multilayered film excellent in adhesion, transparency, heat resistance, flexibility, gas barrier properties, touch properties and cutting properties. The polypropylene multilayered film includes at least a surface layer and an inner layer comprising a gas barrier resin and is stretched at a stretch ratio of 2 or more in a longitudinal or lateral direction and has a tensile elastic modulus of 200-1,000 MPa. In the multilayered constitution of this film, the surface layer comprises a composition prepared by mixing a polypropylene resin, and a softening agent, an adhesion agent and a liquid adhesion auxiliary agent in a proper mixing ratio and the inner layer comprises an ethylene/vinyl alcohol copolymer resin.

Description

570873 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7 V. Description of the Invention () 1 [Technical Field] The present invention relates to packaging for articles, such as packaging films used for food packaging in households and the like. In particular, the present invention relates to a polypropylene-based packaging film having excellent airtightness, adhesion, transparency, tension and elasticity. [Technical background] For food businesses such as grocery stores, food stores, etc., or when storing food in ordinary households or heating in a microwave oven, a film made of thermoplastic resin has been used for a long time. Among them, vinylidene chloride-based polymer resin-based food packaging films are widely used in food packaging films because they have excellent properties such as moisture resistance, air tightness, heat resistance, adhesion to containers, and transparency. . In recent years, films for food packaging made of various non-chlorine resins have also been proposed. For example, polyolefin resins such as polyethylene resin, polypropylene resin, and 4-methylpentene resin are mainly used. Polyolefin resins, such as polypropylene resins, lack sufficient airtightness or have no adhesiveness on the film surface, and the adhesive properties required for films for food packaging are not sufficient. In order to meet such desired characteristics, it is recommended to add various additives, mix other resins, or provide films with other resin layers. Such thin fats, depending on the type of resin used or the type or amount of additives used, and the type of laminated resin, will improve the adhesion and heat resistance of the container, even if it is airtight or adhesive to the container. It affects the vinylidene chloride-based copolymer resin-based packaging film. Therefore, considering the air-tightness of packaging films based on non-chlorine resins, there are Japanese Unexamined Patent Publication No. 6-322194, Japanese Unexamined Patent Publication No. 6-155677, and this paper standard applies Chinese National Standard (CNS) A4 specifications ( 210X297 mm) (Please read the precautions on the back before filling out this page) -4-570873 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _________ V. Invention Description () 2 JP 7-3 0 8 9 However, it is not possible to produce a satisfactory film. For example, in Japanese Unexamined Patent Publication No. 6-3 2 2 1 94, it is produced in a styrene-ethylene-butene-styrene block copolymer having flexibility in an acrylic resin. And a film of a resin composition having a liquid polybutene adhering and adhering to the surface layer. However, liquid polybutene is liquid. If mixed with polyolefin resin, the film becomes soft, and the film loses its tension or elasticity. It is easy to entangle fingers or the package when cutting the film. It is convenient to use as a packaging film. Poor sex. In addition, Japanese Patent Application Laid-Open No. 6-1 5 5 6 77, a film made of a polyolefin-based resin layer containing a tackifier interposed between an acid-modified polyolefin layer on both sides of an ethylene-vinyl alcohol layer, and airtight The characteristics also take into account the easy cut-off. However, in order to achieve good cutting properties, the film is a hard film without softeners. It has a good feel or follows the shape of the package. Only the film flexibility needs to be improved. Japanese Patent Application Laid-Open No. 7-3 0 8 9 is based on the composition of Japanese Patent Application Laid-open No. 6 -3 2 2 1 9 4 which contains a graft-modified polyolefin resin by an unsaturated carboxylic acid or a derivative thereof. The resin composition is a single layer or a multilayer body. This technology also leaves the film soft or difficult to handle when cutting the film. 0 In order to solve such problems, the object of the present invention is to provide air-tightness improvement even when a polypropylene resin with poor air-tightness and adhesion is used. It is easy to use because of its adhesiveness and adhesiveness. It is useful as a thin film of non-chlorine resin thin film. This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling this page) -5- 570873 A7 B7 V. Description of the invention () 3 [Disclosure of the invention] (Please (Please read the notes on the back before filling in this page.) The inventors worked hard to solve the above problems, and completed the present invention. That is, the present invention is as follows. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention relates to polypropylene-based packaging films, which are composed of polypropylene resin 9 9 to 2 0 wt% and softener 1 to 80 0 wt%, for which a total of 1 0 0 The surface layer made of the composition containing 2 to 30 mass parts of the adhesive, the inner layer made of airtight resin, a multilayer film stretched more than twice in the longitudinal direction and / or the transverse direction; the above-mentioned softener At least one selected from the group consisting of amorphous or low-crystalline propylene-α-olefin copolymers and crystalline polybutene-1; at least one selected from the above-mentioned binder systems selected from hydrogenated petroleum resins, hydrogenated terpene-based resins, and Hydrogen rosin resin, liquid polybutene, liquid polyisobutylene, liquid butyl rubber. The present invention relates to a polypropylene-based packaging film, and the softener is at least one selected from the group consisting of styrene-ethylene-butene-styrene, styrene-butadiene-butene-styrene, A block structure copolymer of any of styrene-ethylene-propylene-styrene, styrene-butadiene-styrene, or styrene-isoprene-styrene; at least one of the above-mentioned adhesives is selected from Hydrogenated petroleum resin, hydrogenated rosin resin, hydrogenated terpene resin, liquid polyisobutylene, liquid butyl rubber. [The best form for implementing the invention] The polypropylene resin used in the polypropylene tree composition constituting the surface layer of the present invention is made by the film to have the film's tension, elasticity, ease of use, melt tension during film formation, and stable production. The viewpoint of film properties is more than 20 wt%. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -6- 570873 A7 B7 V. Description of the invention () 4 (Please read the precautions on the back before (Fill in this page) On the other hand, from the viewpoints of softness, tactile feel, and followability of the shape of the packaged product, 99% by weight or less. It is preferably 30 to 9 7 w t%, and most preferably 40 to 9 3 w t%. Within the above range, an appropriate blending ratio may be determined based on the softener described later. The polypropylene-based resin used in the present invention has a propylene unit in the polymer molecular chain, and is a homopolymer made of only propylene units. The units may be stored in the polymer in a block or irregular shape. There are various structures such as random, isotactic, and interregular. All of the above can be used. For example, commercially available propylene is dominated by isotacticity, and some random ones are used as secondary components, and these can also be used. Polypropylene copolymer resins are known as random copolymers or terpolymers with ethylene or butene, and any of them may be used. In particular, it is advantageous to use a terpolymer or a random copolymer for the purpose of adhering flexibility, and a homopolymer is excellent for the purpose of adhering to heat resistance. When used for food packaging films, it is preferable to use polyolefins such as Noblen W 5 3 1 D and Noble F S 2 0 1 1 D manufactured by Sumitomo Chemical that meet the voluntary rules of the Sanitary Association. The melting coefficient of the polypropylene resin printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is based on the method of JIS-K 6 7 5 8 with a load of 2 3 0 t: 2 · 1 6 KG at 1 to 2 0 A range of g / 10 is better. Softeners added to the above polypropylene trees include amorphous or low-crystalline ethylene-? Olefin copolymers and crystalline polybutene-1. Here, the term "low crystallinity" refers to a resin of propylene-alpha olefin copolymer generally referred to as "amorphous" or "low crystallinity" in the industry, and the crystallinity is about 25% or less based on the example of low crystallinity. By. Softeners can also include styrene-ethylene-butene in the molecular chain. The size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 'One 570873 A7 B7 V. Description of the invention () 5 Styrene Block of any of styrene-butadiene-butene-styrene, styrene-ethylene-propylene-styrene, styrene-butadiene-styrene, styrene-isoprene-styrene Structural copolymer. Which one should be selected is to select the appropriate one based on the type of polypropylene resin or adhesive added to the surface layer or the film characteristics. For example, for the purpose of producing moderate softness, when the latter group softener is selected, the above-mentioned adhesive is selected from liquid polybutene. For food packaging, it is advisable to choose, for example, Tafma X R series manufactured by Mitsui Chemicals and Taftech L 5 1 5 manufactured by Asahi Kasei, which conform to the voluntary rules of the Sanitary Association. The so-called amorphous or low-crystalline ethylene-α-olefin copolymer is a copolymer of α-olefins such as ethylene, propylene, butene, and pentene, and propylene, and those having low crystallinity or amorphousness. This type is rich in flexibility by itself, and when mixed with a polypropylene resin, it has the property of not impairing its transparency and producing a softening effect. The crystalline polybutadiene-1 is a homopolymer of butene-1 or a copolymer with propylene or ethylene, which is polymerized in the molecular weight of the cylinder and has a degree of crystallization of about 50%. It is excellent in softness and heat resistance. Liquid low molecular weight polybutylene. Burn. Contains styrene-ethylene-butene-styrene, styrene-butadiene-butene-styrene, styrene-ethylene-propylene-styrene, styrene-butadiene-styrene, or The block structure copolymer of any of styrene-isoprene-styrene (hereinafter referred to as styrene-based block copolymer), the polyethylene part of the rigid segment constitutes a physical cross-linking to form a domain phase, The soft-block rubber elasticity was found in the ethylene-butene part or the ethylene-propylene part. The sequence pattern of self-hard block and soft block is divided into linear kumamoto paper. Applicable to China National Standard (CNS) 8-4 (210X297 mm) (Please read the precautions on the back before filling this page) Γ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-570873 A7 B7 V. Description of the invention () 6 (Please read the precautions on the back before filling this page) and the radial form, both can be used. The above-mentioned block structure ratio of the copolymer can be set according to the desired flexibility. If the hydrogen additive of such a copolymer is used, it can be applied to a film for food packaging from the viewpoint of suppressing the odor of the film. These ethylene-based block copolymers have good compatibility with polypropylene resins. If the appropriate amount is used, the original transparency, moisture resistance, and heat resistance of polypropylene resins will not be impaired, and the tensile elasticity or bending elasticity will be reduced. , Which has the effect of attaching softness. With this packaging film, the stability of the adhesive strength, the followability of the shape of the packaged object, the good feel to the touch, the good adhesion effect when wrapping food, etc., will reduce the production of rigidity when peeled from the container, etc. Tube effect. The added amount of the viewpoint of the flexibility of the self-made film is based on the polypropylene resin and softener; [0 〇W t%, it must be more than 1 W t%. Melt tension during film forming, processability, product Views such as appearance or price, tension, and elasticity are more than 80 W t%. It is preferably 3 to 70 W t%, and most preferably 7 to 60 wt%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on the above-mentioned polypropylene resin. At least one selected from petroleum resins such as hydrogenated petroleum resin, hydrogenated terpene resin, hydrogenated rosin resin, and liquid polymer. Butene, liquid polyisobutylene, liquid butyl rubber. Adding amount ', when the composition made of polypropylene resin and softener is 100 parts by mass, from the viewpoint of adhesion characteristics, it is 2 parts by mass or more, the viscosity of the film, the adhesion between the films, the melt tension, In accordance with the stability of the film during film formation and the deviation in film thickness and film formation properties, when using hydrogenated petroleum resins or hydrogenated terpene resins from the viewpoint of film flexibility and adhesion characteristics, 30 mass parts are required. the following. It is advisable to use 3 quality department to 2.5 quality department, preferably the paper size applies Chinese National Standard (CNS) A4 specification (2 丨 〇 '乂 297 mm) -9- 570873 A7 B7 employee consumption of Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative prints 5. Description of invention () 7 4 ~ 2 2 Quality Department. Here, the so-called petroleum resin refers to a synthetic resin obtained by polymerizing and / or processing C 5 and C 9 fractions obtained by decomposing light oil during petroleum processing, and aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, and aromatic hydrocarbon resins. In addition, a dicyclopentadiene-based resin is mentioned. When used in food packaging films, hydrogenated petroleum resins using such hydrogen additives are required due to the requirements of product safety, price of odor, color, and other properties, as well as the stability of the so-called adhesive properties. In order to improve the pull-out property when the formed film is used as a roll, and to reduce the leakage of low molecular weight components, or from the viewpoint of the touch of the film itself and the convenience of use of the film, the softening point of the ring and ball method is set to 90 ° C or higher is preferable, and from the viewpoint of flexibility and adhesion, it is preferable to be 140 ° C or lower. Terpene resins are homopolymers or copolymers of α-pinene, / 3-pinene, limonene, and dipentene made from pine bark or citrus fruit skin. Various forms of resins exist for the same reasons as above, and it is advisable to use hydrogen additives as food packaging films. The softening point of the terpene resin is preferably 100 ° C or higher from the viewpoint of film stickiness, and from the viewpoint of softness and adhesion of the surface layer part which is matched with it, the temperature is preferably 14 ° C or lower. Hydrogenated rosin resin rosin produced by distillation of turpentine; wood rosin obtained by extracting pine root wood chips and extracting them with solvent; turpentine rosin separated from waste liquid from the production of kraft pulp; etc. Conjugated double-stranded hydrogen addition of Rosin Ting acid. Proper use of hydrogen additives can improve weather resistance or thermal stability, or has a low odor or transparency when added to a film. The softening point of the hydrogenated rosin-based resin is preferably 80 ° C or higher from the viewpoint of film stickiness, and 115 ° C or lower from the viewpoint of flexibility and adhesion. This paper size applies to China National Standard (CNS) A4 specifications (210X297 mmΊ (Please read the precautions on the back before filling out this page) -10- 570873 A7 B7 V. Description of the invention () 8 Polybutene in liquid form At room temperature, the thick liquid or amorphous solid state is transparent or translucent. The copolymer of isobutylene and butene is called liquid polybutene. It is different from the crystallinity formed by polymerizing butene-1 only. High molecular weight polybutene-1 resin. Also, homopolymerization of liquid polyisobutylene-based isobutylene, which is an amorphous semi-solid transparent or translucent liquid with extremely high viscosity at room temperature. Liquid butyl rubber The copolymerization of polyisobutylene to isoprene within 2% is a colorless, odorless, odorless liquid or semi-solid rubber. It is better to add hydrogen to liquid polybutene. The softener is ethylene. In the block copolymerization, the adhesive is other than liquid polybutene. The liquid polybutene and the above-mentioned block copolymer are both soft and have a high softening effect. When the two films are used, the film becomes soft, the film loses tension or elasticity, and is cut off. When the film is used, it is easy to wrap your fingers or the package as a bag. The film is not easy to use. The liquid polybutene is preferably a number average molecule of 300 to 4000, and the liquid polyisobutylene or liquid butyl rubber has an average molecular weight of 2000. It is preferably ~ 600,000. This is appropriately selected according to the purpose of the adhesive force. For example, two or more liquid polybutenes or liquid polyisobutylenes and liquid butyl rubbers having different molecular weights are mixed, and can be adjusted as desired. For molecular weight, if necessary, liquid polybutene and liquid polyisobutylene or liquid butyl rubber can be mixed. Furthermore, without departing from the scope of the present invention, a liquid adhesion promoter can be added for adjusting the adhesion. At least one liquid adhesion promoter is selected from the group consisting of mineral oil, white mineral oil, polyalkylene glycol, alkylene glycol, sucrose fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, and Glycerin fatty acid esters, propylene glycol fatty acid esters, and higher alcohol fatty acid esters. The amount of addition, if the composition made of polypropylene resin and softener is 1,000 parts by mass The Chinese paper standard (CNS) A4 applies to this paper size Specifications (210X 297mm) (Please Read the back of the precautions to fill out this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -11-570873 Α7 Β7 V. Description of the invention () 9 'This is 0. 0 1 The quality department or above can meet the complete adhesion-improving effect. The viewpoint of stable adhesive properties is preferably 30 parts by mass or less. The most preferred range is 0.1 to 25 parts by mass. If it is within this range, the cuttability or feel can be improved. Therefore, the adhesion promoter is liquid, and after dissolving or decomposing it in liquid polybutene and liquid polyisobutylene in advance, polypropylene resin can also be added. The liquid adhesion promoter, by being stored on the surface of the film, expands the wettability of the adherend to enhance the self-adhesion of the film, and the adhesion to the adherent film becomes better. Therefore, it is only necessary to increase the adhesion to increase the content of the liquid adhesion promoter. In addition, the mixed resin has strong adhesive force. If such liquid substances exist on the surface, the area where the adherent substance contacts the adherend is reduced. By using this effect, the film surface adhesive force can be adjusted outside the appropriate range, and the effort required to pull out the roll film can also be adjusted and reduced. In addition, known additives may be mixed in the surface layer formed of the polypropylene-based resin composition without departing from the scope of the present invention. The resin used for the inner layer is excellent in airtightness, for example, an aromatic crystalline nylon such as ethylene-vinyl alcohol copolymer resin or nylon MXD 6, a fatty crystal such as nylon 6, nylon 6 6, nylon 12 and the like. Other than nylon, amorphous nylon can be mentioned. Ethylene-ethylene glycol copolymer resins are, for example, crystalline resins in which ethylene and vinyl acetate are copolyethylene vinyl acetate under high pressure, and monomers are removed, and alkalised with a base such as tartrine, and dried. The ethylene content of the ethylene-vinyl alcohol copolymer resin used in the present invention is preferably from 20 mol% or less from the viewpoint of melt viscosity and film forming processability, and preferably from 50 mol% or less from the viewpoint of air tightness. . For the purpose of ensuring the forming processability, a suitable amount of this paper size can be applied to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the precautions on the back before filling this page), Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumption Cooperatives-12- 570873 Printed by Employee Consumption Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7___ V. Invention Description (10) Cooperating with well-known plasticizers can be used without compromising the original air-tightness or related fragrance protection. The scope of sex. A suitable blending amount is 100 parts by mass or less for the ethylene-vinyl alcohol copolymer resin. Nylon MX D 6, such as a thermoplastic crystalline resin made from m-xylylenediamine and oxalic acid, has an aromatic ring in the molecular chain structure. Nylon 6, for example, a thermoplastic resin produced by ε-caprolactam ring-opening polymerization or ω-aminocaproic acid polycondensation is excellent in airtightness. Nylon 66, for example, a thermoplastic resin produced by the polycondensation of 1,6-hexanediamine and adipic acid; nylon 12, for example, using butadiene as the starting material to produce cyclododecatriene, Eleven Store's is used to prepare laurylamine, and then it is produced by ring-opening polymerization, or cyclohexanone is used as the raw material to produce aminododecanoic acid through p-amine, cyanodecanoic acid, and then polymerized. This is to make a thermoplastic resin. A non-crystalline nylon with an aromatic ring in the molecular chain structure of amorphous nylon. A resin with low water absorption and excellent air tightness. The purpose of these resins is to ensure molding processability or to ensure properties when used in food packaging films, for example. A suitable amount of a known additive may be blended, and there is no particular limitation on the melt index or melting point of the nylon resin itself. In addition, as long as the surface layer and the inner layer in the multilayer structure do not interfere with the purpose of the present invention, an adhesive resin layer using a known resin composition, or a remanufactured layer such as a punched end at the time of production can be arranged. In addition, a polypropylene-based resin layer for adjusting various physical properties such as thickness, flexibility, and heat resistance may be disposed. For example, a polypropylene-based resin disposed between the surface layer and the adhesive layer may be a composition layer composed mainly of Use the same polypropylene resin as the surface layer for the polymer. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page)-1 m J .. -13 -) / ⑽73 A7 B7 V. Description of the invention (11) The resin with propylene units in the molecular chain is suitable. The configuration of the propylene units in the molecular chain can be block or irregular, and only homopolymers can be composed of propylene units. 〇 It can be used for various structures such as random, isotactic, and interregular. For example, commercially available propylene is dominated by isotacticity and mixed with some random as a secondary component, and these can also be used. Copolymer resins are generally known as random copolymers or terpolymers, such as ethylene and butene. Additives are preferably free of slip agents or anti-blocking agents. In the case of a film for food packaging, from the viewpoint of safety, it is preferable to use, for example, polyolefins made by Sumitomo Chemical, such as Noblen W 5 3 1 D, Noblen FS20 11D, and the like, which conform to the voluntary rules of the Sanitary Association. The melting coefficient of polypropylene resin is preferably in the range of 1 to 20 g / 10 minutes at 230 ° C and 2.16 KG load state according to the method of J IS — K 6 7 5 8 standard. The tensile elastic modulus of the film as a whole is preferably 2000 to 1000 MPa. This is based on the method contained in ASTM-D-882. Tensile elasticity when the longitudinal direction (MD-stretching direction) and transverse direction (direction perpendicular to the TD-stretching direction) of the film of the tensile testing machine is deformed by 2%. The rate is average. Within this range, the film is excellent in softness, tension, and elasticity, and is excellent in softness and adhesion. It is preferable that it is 4 0 MP a or more and 70 OMP a or less. The adhesiveness of the film was adhered to the glass plate using a load roller with a mass of 2 kg and a width of 45 mm in accordance with the method set forth in JIS-Z-02 3 9 and a 90-degree peel test. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -14-570873 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () 12 degrees 値 It is better to be above 0 · 7cN, preferably 1.5Cn Above, the upper limit for the film to be easily pulled out is 4 c N. If excellent pull-out property is required, 3 c N or less is preferable. The softening agent or adhesive selected for the tensile elastic modulus or adhesiveness in the above range can be achieved by appropriately combining a liquid auxiliary liquid or a polypropylene resin depending on the situation. For example, a combination of amorphous or low crystalline ethylene-vinyl alcohol and liquid polybutene in a quantitative amount 'or a combination of styrene-ethylene-butene-styrene and a hydrogenated petroleum resin with mineral oil is preferred. The structure ratio of the overall layer. When the thickness of the entire layer is 100, take the 5-layer structure of the surface layer, the adhesive layer, the inner layer, the adhesive layer, and the surface layer as an example. Adjust the two surface layers to 50 to 90 and the two adhesive layers to 5 to 30. The inner layer is preferably within a range of 5 to 25. Take the surface layer, polypropylene-based composition layer, adhesive layer, inner layer, adhesive layer, polypropylene-based composition layer, and 7-layer structure of the surface layer as examples. Adjust the two surface layers to 5 ~ 20, two The polypropylene-based composition layer is preferably within a range of 40 to 85, the two adhesive layers are 5 to 20, and the inner layer is within a range of 5 to 20. The thickness of the two surface layers or two adhesive layers may be different, but to distinguish between the surface and the surface of the film, it is better to use the same thickness. The thickness of the thin body as a whole, from film strength, tension or elasticity, softness and air tightness during packaging. The viewpoint is preferably less than 3 // m, and the viewpoint of adhesion to the article when it is packaged, the quality of the product when it is a roll, the diameter of the roll, and ease of handling during use is preferably less than 2 5 // m. In particular, the airtightness, softness, and balance of followability of the packaged object are preferably 6 // m to 1 5 // m. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-15- 570873 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () 13 For the method of manufacturing the film of the present invention, a known film forming method can be used. The surface layer polypropylene resin composition is prepared by melt-kneading using an extruder. Softeners and adhesives are granular, granular, flake, or powder. If they are solid, they are mixed with commercially available polypropylene resin granules at the same amount into a mixer, etc., and mixed thoroughly. It can also be put into the surface layer using an extruder at an appropriate temperature to knead it into a homogeneous composition, and extruded from a laminated adhesive layer such as a multilayer die or an inner layer into a multilayer film. Such a sufficient melting and kneading can also be carried out into granules using a granulator by a known method, and then put into an extruder for a surface layer. When the film has the function of adding liquid additives to the film, there is also a method of coating the film after forming. For example, it can be poured in the melting zone of a uniaxial extruder or a biaxial extruder using a pressurized liquid pump. Kneaded in molten resin. The inner layer is prepared with raw materials. If granules such as ethylene-vinyl alcohol resin or nylon resin are used as they are, no special steps are required. When the plasticizer is added, they are mixed by a mixer and then put into the extruder for the inner layer. Regarding the adhesive layer, the raw materials are prepared with the same concept. In order to manufacture a multilayer structure film, a five-layer structure including an adhesive layer is used as an example, and an extrusion machine for an adhesive layer and an inner layer are arranged in parallel with the above-mentioned extrusion machine for the surface layer. Downstream measurement combines the resin from the extruder into five layers. For example, a ring-shaped die or a T-die with a slit-shaped discharge port is used to extrude and form a sheet. The extruded resin is solidified by cooling in a cold water tank or by contacting a cooling roller. The sheet obtained by extrusion is stretched in a longitudinal direction and / or a transverse direction by a known method, that is, a tenter method or a blow molding method. From the viewpoint of the strength of the film and the cut-off property for packaging films, the paper dimensions in the vertical and / or horizontal direction apply the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before reading) (Fill in this page)

-A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () 1 14 1 I Stretched more than 2 times 〇 If the tenter method is used, the stretching sequence in the vertical and horizontal directions is not equal to 1 | It is also possible to have different magnifications in the vertical and horizontal directions. □ Stretch the film of I, and cut or cut the end to the desired size. When the film is rolled, please roll it first. Twisted around the tube, etc. j Read the back according to the shape of the product 1 Note that the product 0 is passed through the steps. 薄膜 The film produced according to the present invention has adhesiveness, transparency and heat resistance. 1 item 1 I Good softness, airtightness 、 Moisture-proof, cut-off, safety #% i 1 Excellent. This film is suitable for use as a film for household food packaging. 0 copies < page'—✓ 1 I [Example] 1 1 1 Next example Embodiments of the invention 〇 Any form 1 of the present invention 1 Order 1 I > Not limited to such examples 〇 The method for evaluating the properties of the film prepared according to the present invention is as follows 0 1 1 1 Evaluation of adhesion 9 According to J IS-Z — 0 2 3 7 Loaded method 1 1 Standard 9 Using a load roller with a mass of 2 kg and a width of 4 5 mm to attach a film with a width of 2 0 to a line mm to a glass plate y Peel strength when performing a 90 ° peel test »Degree 値 (Ρ) 1 • 5 CN is A, 7 CN or more 1 • 5 c N or less 1 1 I is B 0 • 3 CN or more 0 • 7 c N or less is C 0. 3 CN 1 or less is D 0 1 Transparency according to AST M -D — 1 0 3 of the method described in the standard 1 using ND κ-3 0 0 A (made by the Japanese electrochromic) to determine the turbidity of the film 1 I degree (() 5 its measurement 値 1 • 0 below is A 1 0 or more 2 • 0 1 1 I or less is B 2 • 0 or more 0 • 3 or less is D 0 1 1 Heat resistance 1 According to the Tokyo Metropolitan Consumer and Living Regulations Chapter 1 1 , Heat-resistant temperature 1 1 This paper size applies to Chinese national standards (CNS> A4 size (210X297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 570873 A7 B7 V. Description of the invention () 15 degrees (T) 1 4 0 ° Films above c are A, 130 ° C to 135 ° C are B, and 125 ° C or lower are D. Softness, according to the method contained in ASTM- D-8 8 2 using a tensile tester to determine the elastic modulus of the film when the longitudinal direction (MD) and transverse direction (TD) are deflected by 2%, the average of both sides値 (Μ) A below 400 MPa and 700 MPa below is A, 200 MP a and above 40 OMP a and below 70 OMP a and above 100 MPa B, 100 MPa and 200 MPa and below are C, 100 MPa and below or 1000 MPa and above D. Hand feeling, randomly selected a predetermined number of housewives 50, feel good, poor, and perform sensory evaluation. The number of people who think it is good (N) 4 5 or more

A, 40 or more are B, 30 or more are C, and the other is D o air tightness, according to the method of AST M-D-3 985 standard using No. 0 Co.)) X- TRAN200H measures the barrier property to oxygen. Under atmospheric pressure, the temperature is 2 3 ° C and the humidity is 65. (B) 200cm3 / m2 · 24hr s. A tm. 1 1 / zm and below, A, 200cm3 / m2. 24hr s. atm. ll // m or more 500cm3 / m2. 24hrs .a tm · 1 1 / zm or less is B, 500cm3 / m2 · 24hrs. atm. ll // m or more is D. The cut-off property of the film. The prepared film was rolled on a paper tube with a width of 300 mm and a roll length of 10 mm. The packaging for food packaging was rolled back for processing, and then this ^ paper size was applied to the Chinese National Standard (CNS) A4. Specifications (210X297mm) Series-1R- (Please read the precautions on the back before filling this page)

570873 B7 V. Description of the invention (16) Cut with a saw attached to a commercially available cosmetic box for household packaging. Since the current cutting state, A is light, that is, a clean cut is required, and some force must be used. B can be cleanly cut, C that can be cut but difficult to cut, and C, which cannot be cut.

The film is stretched, or slightly damaged, or the cosmetic case is damaged due to excessive force. D is summarized as shown in Table 1. Any evaluation item is judged to be the best for A, and B or more is practical. C and D have Practical issues. Table 1 Evaluation item unit ABCD Adhesion cN 1.5 ^ P ^ 4 0.7 ^ P < 1.5 0.3 ^ P < 0.7 Ρ < 0 · 3 Transparency% Η < 1 · 0 1 · 0 $ Η < 2 · 0 2 · 0 ^ Η3.0 3.0 ^ Η Heat resistance ° C 140 $ TT = 130 or 135-125 Softness MPa 400 S M < 700 200 ^ M < 400 or 700 ^ M < 1000 100 ^ M < 200 Airtightness outside the left column cm3 / m2 · 24hrs · atm · 11 // m B < 200 200 ^ B < 500-500 ^ Β Hand feeling number 45 ^ N 40 ^ N < 45 30 ^ N < 40 Ν < 30 Clean cutting requires some force. Clean cutting is possible. Cutting is difficult, but it is difficult to cut off the left column. [Example 1] Polypropylene resin (Noblen W 5 3 1 D manufactured by Sumitomo Chemical, propylene-ethylene-butene random three) Copolymer, MFR = 9 g / 1 0 points), softener is styrene-ethylene-butene-styrene block copolymer resin (manufactured by Asahi Kasei Industries, Taftech L 5 1 5), and the binder is hydrogenated This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page) Thread Printing Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative, printed 570873 A7 _ B7_ V. Description of the invention (17) Cyclopentadiene-based petroleum resin (made by Pellet Petrochemical, Marcull l 925C). The polypropylene film and softener have a mass ratio of 80 ... 20, and a total of 100 parts by mass and 5 parts by mass of the adhesive are blended. Put into the mixer and mix thoroughly at room temperature for 5 minutes. The mixed granules were put into three layers of a five-layer extruder device for a surface layer, an adhesive layer, and an inner layer. An acid-modified polypropylene-based adhesive resin (Mitsui Chemical Co., Adma QF570) and an ethylene-vinyl alcohol copolymer resin (Clare, Evarl EP-S124B) were melt-kneaded in each of the extruder and used. Multi-layer annular die is laminated and extruded into 3 kinds of 5 layers of film at a temperature of 220 ° C. The obtained film is blow-molded into a stretching device, and stretched 5 times in the longitudinal direction at a stretching temperature of 120 ° C and 4 times in the transverse direction. After that, the edges of the edge film were trimmed to obtain a homogeneous film having an overall thickness of 1 1 / zm. For the thickness of each layer, when the thickness of the entire layer is 100, the order of the surface layer, the adhesive layer, the inner layer, the adhesive layer, and the surface layer is 3 5, 10, 10, 10, 35. After measuring the physical properties of this thin film, it showed good characteristics as shown in Table 2. [Example 2] Regarding the resin composition of the surface layer of Example 1, the same as Example 1 is a polypropylene resin, and the same styrene-ethylene-butene-styrene block copolymer resin as in Example 1 is used at a mass ratio of 9 In a ratio of 5 to 5, when this is 100 parts by mass, in addition to the adhesive of Example 1, mineral oil (Matsumura Petroleum, Smill P 7 0 >) of 100 parts by mass is added as a liquid adhesion promoter. . Other thicknesses of 1 1 # m are made in the same way as in Example 1. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) (Please read the precautions on the back before filling this page). Order -Line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 570873 A7 ___B7 V. Description of Invention () 18 film. After measuring the physical properties of this film, the good characteristics shown in Table 2 are shown. [Example 3] In the resin composition of the surface layer of Example 1, a polypropylene resin and a softener were added in an amount of 100 parts by mass, and 5 parts by mass of mineral oil (Matsumura Petroleum, Smill P 7 0) was added as a liquid adhesion promoter. . Otherwise, the same method as in Example 1 was used to obtain a film having a thickness of 1 1 // m. After measuring the physical properties of this film, as shown in Table 2, good characteristics were shown. [Example 4] Except for the resin composition of the surface layer of Example 2, the liquid adhesion promoter was changed to a fatty acid triglyceride (manufactured by Vitamin, Actor L01) of 10 parts by mass. A thin film having a thickness of 11 μm was prepared in the same manner. After measuring the physical properties of this film, the good characteristics shown in Table 2 are shown. [Example 5] The mass mixing ratio of the polypropylene resin and homopolypropylene (made by Sumitomo Chemical, Noblen FS20 1 ID, MFR = 2 / 5g / l 0 points) in Example 3 as a softener was changed to 70: 3 Other than 0, a thin film with a thickness of 1 1 // m was prepared in the same manner as in Example 3. The physical properties of this thin film were measured and shown in Table 2 to show good characteristics. [Example 6] This paper size is in accordance with Chinese National Standard (CNS) 8-4 specification (210X297 mm) " " " 丨 丨 .1 丨 丨. # 1 (Please read the precautions on the back before filling this page )-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-91-570873 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () 19 Change the adhesive of Example 3 to hydroterpene Resin (manufactured by Yasuhara Chemical Co., Ltd., Clearon P125) except for 15 parts by mass. In the same manner as in Example 3, a film having a thickness of 1 1 // m was obtained. The physical properties of this film were measured and shown in Table 2 to show good characteristics. [Example 7] The softener in Example 3 was changed to a low-crystalline propylene-α-olefin copolymer resin (Mitsui Chemical Co., Tafma XR110T), and the binder was a liquid hydrogenated polybutene (manufactured by Japan Oils and Fats, Nissan Poly Except for butene 1 0 S)) 10 except for the mass part, a thin film having a thickness of 1 1 // m was prepared in the same manner as in Example 3. The physical properties of this film were measured and shown in Table 2 to be good. [Example 8] Except that the thickness obtained in Example 2 was changed to 20 / m, the film was prepared in the same manner as in Example 2 and the good characteristics shown in Table 2 were shown in Table 2. [Example 9] In the surface adhesive of Example 7, a hydrogenated rosin resin (forged by Hercules, FORAL 105) was used in place of 10 parts by mass of liquid hydrogenated polybutene (manufactured by Nippon Oil & Fat, Nissan Polybutene 10SH). 7 The same method was used to produce a film with a thickness of 1 1 // m. The physical properties of this film were measured and shown in Table 2 to show good characteristics. This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page)

、 1T -22- 570873 A7 B7______ 5. Explanation of the invention () 20 [Comparative Example 1] After using the composition of Marcull H925C as the surface layer in Example 1 to form the surface layer, the characteristics shown in Table 2 are obtained. [Comparison Example 2] After forming the surface layer without using Taftech L515 of Example 1 as the softener composition of the surface layer, the characteristics shown in Table 2 were obtained. [Comparative Example 3] The ethylene-vinyl alcohol copolymer resin Evral of Example 1 was not used. EP-S 1 2 4 B is the inner layer resin. After the film is composed of only the surface layer and the adhesive layer, the characteristics shown in Table 2 are obtained. [Comparative Example 4] After forming the surface layer without using the composition of Marcull H925C as the surface layer adhesive of Example 3, the characteristics shown in Table 2 were obtained. [Comparative Example 5] After the surface layer was composed of 50 mass parts in Maixull (R) 9 2 5 C, which was used as the surface layer adhesive in Example 3, the wound film produced blocking during storage. When the film was stored without being wound by using the film, the characteristics shown in Table 2 were obtained by evaluating the characteristics. For the reasons described above, since the film cannot be easily pulled out in the state of the wound paper tube, the cutability cannot be evaluated. This paper size applies to Chinese national standards (CNS > A4 size (210 X 297 mm) | 丨 .J —— < ---- # 1 (Please read the precautions on the back before filling this page), 1T line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -23- 570873 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (21 [Comparative Example 6] The amount of Taftech L515 used in Example 3 is 90wt% After being used as a surface layer softener, the extrusion of the surface layer resin is unstable, and a film with good appearance cannot be obtained. [Comparative Example 7] The amount of Smill P 7 0 used in Example 3 was 4 5 After the film was prepared in the same manner as in Example 3 except for the agent, the melt tension of the resin in the surface layer was too low to stably squeeze, and an evaluable film could not be obtained. [Example 8] The surface layer adhesive of Example 7 was used Ethylene-α-olefin copolymer Shugeki (Mitsui Chemical Co., Ltd. Tafma P 0 6 8 0) instead of propylene-α-olefin copolymer resin, except that a film was prepared in the same manner as in Example 7 and obtained as shown in Table 2. The characteristics. [Embodiment 9 ] The surface softener of Example 7 was replaced with a styrene-ethylene-butene-styrene copolymer resin (manufactured by Asahi Kasei Industries, Taftech L 5 1 5) instead of the propylene- ^ olefin copolymer resin. After making the film in the same way, the characteristics shown in Table 2 are obtained. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

-24- 570873 A7

B 2 2 X --- Explain clearly the printed example of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ON <-8 0 wt% XR110T 20wt% 〇m 2 _ (〇 o fin -1 < — 5 Quality Department c < c < < < 〇〇 <-9 5 wt% L515 5 wt% ^ M _ift insert 〇 &d; d PQ < < cmc BU XR110T 20wt% i_ Ι-, Η—o < PQ < < d < PQ V £ > Q 沴 on > S 0 more OO L515 20wt% P125 15 mass department < < < c PQ < FS2011D 7 0wt% <-30wt% P70 5 Quality Department PQ < < < c < < c inch < r- 95 wt% <-5 wt% L01 10 Quality Department < d < < < < c < CO < r ~ 80 wt% 20wt% P70 5 mass section < C < < < c < c (N <-95 wt% 5 wt% P70 10 mass section C < < < c < < T—Η Qrash on > € 0 more than 00L515 20 wt% ^ Μ W soil | QF570 I FP- S124B PQ < < < cc < polypropylene softener adhesive liquid adhesion promoter Inner layer of the adhesive layer I Adhesiveness I Transparent heat resistance Softness Air tightness Tactile cut-off --- --- ------- 0-I (Please Read the notes on the back and fill in this page again.) The booklet paper is again applicable to the Chinese National Standard (CNS) A4 specification (21 OX 297 mm) A7 570873 __B7 V. Description of the invention U3) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs system

On L515 <-C c PQ CJ c Q o 〇 ^ 〇〇 ^ ffi _ m ητίπτίΐ 〇〇1 Ο 〇Ph csl gtt insert 〇 Η 1 ft uo UQ PQ u CQ UQ _ mmm 卜 丄 _ (IS K ~ fe tender 〇〇〇〇CSI fangui 忉 mmrn% 〇Η i & 〇On Κ-fe »锘 归 以 u Μ 镒 2 1« plug UUQQ < 〇1 w 〇v〇m PQ inch following g _: inch 〇q Q < < < c PQ ^ ¢ (W -Η 00 CO ^ > t > 壊 PQ < PQ < Q < CC ο cs 〇 ^ CSI Destruction_ £ »Weng: Q < < Q < d QCQ 〇PQ 「1 ^ T-ΗCO 4- > eg ir > t > PL, Q < < < < PQ 〇〇〇〇〇〇〇 S S Adhesive _ Inner layer ti # 1 m #im #i ti 1Ε 1 is called Φ W loses 1 is called 13 Tortoise 鳏 鳏 Hf —IJII, # 1— (Please read the precautions on the back before filling this page)

* 1T-line · This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) One: U One printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 570873 A7 __B7_ V. Description of the invention () 24 (Note) W 5 3 1 D = Noblen W 5 3 1 D, FS2011D = Noblen FS 2 0 1 1 D, L 5 1 5 = Taftceh L 5 1 5, XR 1 1 0 T = Tafma XR 1 1 〇T, P 0 6 8 0 = Tafma P 0 6 8 0, H 9 2 5 C = Marcull H 9 2 5 C, P 1 2 5 = Clearon P 1 2 5, 10SH = Polybutene 10SH, QF 5 7 0 = Adma QF 5 7 0, EP — S124B = Evarl EP — S124B, P 7 0 = Smill P 7 0 L 0 1 = Actor L 0 1 The present invention will be described in detail with reference to a specific embodiment, in order to make it clear to those skilled in the art without departing from the present invention. Spirit and scope plus various changes or amendments. [Industrial Applicability] The film according to the present invention can provide a polypropylene-based packaging film having excellent adhesiveness, transparency, heat resistance, flexibility, air tightness, handle, and cutting properties. This film is suitable for food packaging films. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-27-

Claims (1)

570873 92, 4ΛΊ Α8 Β8 C8 D8 ★ 、 Patent Application No. 901 29076 Patent Application Chinese Patent Application Amendment April 17, 1992 Amendment 1 · A polypropylene packaging film, which is characterized by: Acrylic resin 9 9 to 20% by weight and softener 1 to 80% by weight. A total of 100 parts by mass and 2 to 30 parts by mass of the composition of the adhesive are formed of a surface layer made of an airtight resin. The inner layer is a multilayer film that extends from 2 times to 8 times in the longitudinal direction and / or transverse direction; the softener is at least one kind selected from amorphous or low crystalline propylene-α olefin polymer and crystalline polybutene Ene-1; This adhesive system is at least one selected from the group consisting of hydrogenated petroleum resin, hydrogenated terpene resin, hydrogenated rosin resin, liquid polybutene, liquid polyisobutylene, and liquid butyl rubber. 2. The polypropylene-based packaging film according to item 1 of the patent application range, wherein the tensile elastic modulus is 2000 to 100 MPa. 3. · A kind of polypropylene-based packaging film, which is characterized by having a polypropylene-based resin 99 to 20 wt% and a softener 1 to 80 wt%. A total of 100 mass parts 2 to 30 mass parts The surface layer made of the composition of the adhesive, the inner layer made of air-tight resin, a multilayer film that extends from 2 times to 8 times in the longitudinal direction and / or the transverse direction; the softener is at least one kind selected from The molecular chain contains styrene-ethylene-butene-styrene, styrene-butadiene-butene-styrene, styrene-ethylene-propylene-styrene, styrene-butadiene-benzene · ethylene, Or styrene-isoprene-styrene block structure copolymer; this paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) Ί ---------- (Please (Please read the notes on the back before filling this page) Order the printed 570873 A8 B8 C8 D8 from the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 々 Application scope of the patent. This adhesive is at least one selected from hydrogenated petroleum resin and hydrogenated rosin. Resin, hydroterpene-based resin, liquid polyisobutylene, liquid butyl rubber. 4. If the polypropylene-based packaging film according to item 1 or 3 of the scope of patent application, the total amount of polypropylene resin and softener containing the surface layer is 100. The mass part is 0 · 0 1 ~ 3 0 Adhesive, the liquid adhesion promoter is at least one kind selected from mineral oil, white mineral oil, polyalkylene glycol, alkanediol, sucrose fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester , Polyglycerol fatty acid esters, propylene glycol fatty acid esters, higher alcohol fatty acid esters. 5 · If the polypropylene-based packaging film of item 1 or item 3 of the patent application scope, wherein the inner air-tight resin is an ethylene-vinyl alcohol copolymer resin. 6. The polypropylene-based packaging film according to item 4 of the application, wherein the inner layer of the air-tight resin is an ethylene-vinyl alcohol copolymer resin. 7 · If the polypropylene packaging film of item 1 or item 3 of the patent application scope, the overall thickness of the film is 3 ~ 2 5 βηι. 8. The polypropylene. Storage packaging film of item 1 or 3 of the scope of patent application, wherein the film adhesion is 0.7 ~ 4cN. T ---------- (Please read the notes on the back before filling in this page) 1T. The paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese national standard (CNS) A4 specification (210X297) Mm) winter