TW490392B - Laminate film having gas barrier property - Google Patents

Abstract

The present invention relates to a laminate film consisting of a two-axis extended polypropylene film and a gas barrier polymer layer laminated onto at least one surface thereof. On the direction of the mechanical axis of said film and the direction perpendicular thereto, the heat contraction ratios at 150 DEG C are both smaller than 5%. Based on the use of the two-axis extended polypropylene film, the laminate film can eliminate the badness in appearance and finish, the drop in oxygen barrier properties accompanied with the badness, as well as the drop in gas barrier properties due to wrinkles resulted from the heat melt at the time of manufacturing a bag.

Description

490392 A7 B7___ V. Description of the invention (1) The present invention relates to a novel laminated film using a biaxially stretched polypropylene film (hereinafter referred to as an OP film under K). More specifically, it is a laminated film that has excellent gas barrier properties (gas impermeability) to oxygen, water vapor, nitrogen and other gases (gas impermeability) and good appearance. It is very useful for gas barrier films used in food packaging. . OPP film has good processing suitability, excellent mechanical strength, transparency, moisture resistance, bag-making properties, and other secondary processing properties, so it is widely used as a packaging film. The above-mentioned OP film, especially in the gas barrier properties, will reduce the gas barrier properties against oxygen. When the properties of the above packaging applications are required, for example, there is a problem in the use of food packaging, that is, curved flask food packaging applications. Therefore, in order to make the OPP film have a gas barrier function such as oxygen, the surface of the OPP film is laminated with a fluorene molecule made of a water-soluble polymer such as a chlorinated ethylene resin or a polyethylene glycol resin. Gas barrier layer. In addition, in order to provide a higher degree of gas barrier properties, it is disclosed in Japanese Patent Laid-Open No. 4-34584 1, Japanese Patent Laid-Open No. 8-9-9390, Japanese Patent Laid-Open No. 9-27896, Japanese Patent Laid-Open No. 9-29 1 25 Et al. Revealed that a sclerosing composition composed of an inorganic polymer obtained by polycondensing a metal alkoxide by a sol-gel method and a polyethylene glycol-based resin is formed by a composite polymer layer formed by thermal curing and M condensation. Polymer gas barrier is laminated on a laminated film made of a thermoplastic resin film. However, the laminated film obtained by laminating the above-mentioned polymer gas barrier layer on an OP film, when hot-melted and bag-made, may cause a break on the molten surface, and may reduce the gas barrier properties of the bag as a packaging bag. -3-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) X .—; ---- !! (Please read the notes on the back to write this page) Order——I- ----

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 490392 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ B7___ V. Description of the Invention (2) In addition, the above compound as a polymer gas barrier layer was formed on the surface of the 0PP film In the case of a polymer layer, the film may cause shrinkage, shrinkage, and damage to the composite polymer layer of the cured film during heat treatment, and may reduce the gas barrier properties of the resulting laminated film, causing problems such as poor appearance. Therefore, the object of the present invention is to provide a MOP film as a substrate and a laminated film having a polymer gas barrier layer laminated thereon, which can solve the appearance and processing problems caused by using the OPP film. The problem of reducing gas barrier properties, and the wrinkles generated by thermal melting during bag making, reducing the problem of gas barrier properties of packaging bags, and having excellent characteristics of laminated films. Other objects and advantages of the present invention will be apparent from the following description. In order to achieve the above object, the present inventors have made intensive studies. As a result, it was found that the use of an OPP film having a thermal shrinkage ratio in a specific range as a substrate, and stacking a polymer gas barrier layer thereon can solve the above-mentioned problems and complete the present invention. In other words, the laminated film of the present invention is specifically a biaxially stretched polypropylene film having a thermal shrinkage of 15% or less in the mechanical axis direction (ND) of the film and the direction (TD) perpendicular to the film, and The tritium molecular gas barrier layer is formed by laminating at least one side thereof. In addition, a preferred aspect of the present invention is to provide a laminated film which further improves the adhesion of the polymer gas barrier layer and has more excellent gas barrier properties and durability. In other words, a preferred form of the present invention is to provide a surface of an OP film with a polymer gas barrier layer laminated thereon, and apply a corona discharge treatment and / or a flame and the like in a nitrogen and / or carbon dioxide atmosphere. ^ ν ·· — · _ϋ 1ΗΙ tat ϋ ϋ-, V (please read the precautions on the back first _ equipment-W write this page) «.

Hi · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 490392 A7 ____B7__ 5. Description of the invention (3) Laminated laminated film. The surface of the 0PP film on the side of the polymer gas barrier layer is subjected to a corona discharge treatment and / or a flame treatment such as a flame under a nitrogen and / or carbon dioxide atmosphere, and a layer with a thickened coating is formed on the surface. film. M and ③ The 0 PP film on the side of the laminated polymer gas barrier layer has at least one polyolefin selected from the group consisting of acid-modified polyolefin, ethylene-containing polyolefin, and butene-1-olefin-containing polyolefin. After the layer is formed, the surface of the layer is subjected to a lamination film of corona discharge treatment and / or plasma treatment such as flame under a nitrogen and / or carbon dioxide atmosphere. In addition, the present invention also provides a laminated film in which various polymer resins are laminated on top of a polymer gas barrier layer on an OP film to improve durability and gas barrier properties.啻 腧 ρρ thin _ ρρ film is used as the base film in the present invention. In other words, the 0PP film has an excellent mechanical strength due to the structure of polypropylene molecules aligned by biaxial stretching, and especially has excellent gas barrier properties for water vapor, and a polymer gas barrier layer laminated thereon. The combination can show a high level of total gas barrier properties. The important requirement in the present invention is the use of the OPP film used as the above-mentioned substrate film, and the thermal shrinkage ratio (hereinafter referred to as thermal shrinkage ratio) in the TD direction of 150 ° 0 and 10 is all 5 × KM. In other words, if the above thermal shrinkage is greater than 5¾, it will be formed as a polymer. -5- This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm)

0 ^ 1 -Is ^^ 1 ϋ— nllf J} (Please read the precautions on the back L Pack--'TV write this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-490392 A7 _B7___ V. Description of the invention (4) During the heating of the following composite polymer layer of the nozzle layer, the degree of shrinkage due to thermal shrinkage increases, and the appearance of the resulting film is poor, or the gas barrier properties may be reduced. In addition, wrinkles are likely to be generated when hot-melted, resulting in a reduction in gas barrier properties of the obtained packaging bag. In addition, in the above-mentioned publications, although it is disclosed that a polypropylene film is used as the base material of the laminated polymer gas barrier layer, the above-mentioned various problems occur in the laminated film using the 0 P P film. In other words, K does not know the problem to be solved by the present invention at all, so this solution is the first proposed by the inventors. The thermal shrinkage of the upper 0 P P film must take into account the appearance or gas barrier properties of the laminated film, and both MD and TD directions are under 5! KM, M 45KK is better, and the better is lower. The thermal shrinkage of the OP film in the present invention is shown in the following examples. The method described in JIS C2318 is used as a reference to measure the thermal shrinkage of MD1 and TD in 1501C. The OP film used in the present invention is only required to have the above-mentioned thermal shrinkage ratio, and there are no restrictions on other characteristics. However, the type of the raw resin constituting the film and the manufacturing conditions are used to select excellent mechanical properties and moisture resistance. And secondary processability of the laminated film are preferred. For example, when the OPP film used in the present invention is measured by the peak apex of differential scanning calorimetry (hereinafter referred to as DSC) (hereinafter referred to as the melting point of the OPP film), when considering the heat resistance or moisture resistance of the film, M 160 ~ 18〇υ is better, more preferably 165 ~ 180 ° C. If the melting point of the above-mentioned OPP film is less than 160 t, the heat shrinkage rate will change -6- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

—Rm ^^ 1 Hi If ^^ 1 I nn _ (Please read the notes on the back J outfit-I π write this page) Order: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 490392 Amendment date A7 90 · 11 · -6 Complement B7_… 丨 · —......... 1 15. The description of the invention (5) is large. In order to achieve the above-mentioned heat shrinkage rate, there is a tendency to reduce moisture resistance. seek. In addition, if it is higher than 180 ° C, it is not easy to manufacture OPP film, so it is not desirable. The polypropylene resin constituting the OP film in the present invention is a conventionally used material, and is not particularly limited. Examples include random or block copolymers of α-olefins other than propylene, such as propylene monopolymer, ethylene, 1-butene, 1-pentene, 1-hexene, and 4-methyl-1-pentene, and propylene , And mixtures of these polymers. Among the above-mentioned polypropylene resins, in order to achieve the thermal shrinkage and melting point suitable for the above-mentioned OP films, the copolymerization ratio of the α-olefins other than propylene M of the polypropylene resin used is preferably 2 mol S: M or more At 1 mole%. The most preferred resin is a propylene monomer. In addition, the above-mentioned polypropylene resin is a highly crystalline polypropylene resin (M with an isotactic pentad fraction measured by 13 C-NMR and having a crystallinity of 0.950 to 0.995, more preferably 0.97 to 0.990. (Hereinafter referred to as highly crystalline PP resin). When the above-mentioned pentad fraction is less than 0.950, problems such as a decrease in the melting point of the OPP film, a high heat shrinkage rate, and a decrease in moisture resistance are easily caused. On the other hand, if it is more than 0.995, the stretch processability at the time of manufacturing the OP film is reduced. The above isotactic pentad fraction is a three-dimensional configuration of 5 consecutive propylene units based on the assigned peak of the W 13 C_NMR spectrum published by Macrozacules et al. Macromolecules 13, 267 (1980). The above-mentioned polypropylene resin can be obtained by a known manufacturing method. For example, the above-mentioned polymer is polymerized using a conventional polymerization catalyst for polypropylene, such as T i C 1 3, a carrier T i C 1 3, an aromatic cycloolefin metal derivative-based catalyst, and the like. National Standard (CNS) A4 Specification (210 X 297 mm) V-^ ------- Installation -------- Order --------- (Please read the first Note: Please fill in this page again.) Printed clothing for employees ’cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 490392 A7 B7 ρ $ ι Method of Inventive Description (and after polymerization, you can also use peroxide, etc. if necessary. Decompose. (Please read the precautions on the back before filling in this page) The measured peak apex value (melting point) of the DSC of the polypropylene resin mentioned above, considering the heat resistance of the film M 1 5 5 ~ 1 6 5 ° C is preferred The more preferable is 16 0 to 16 5 υ. The polypropylene resin having this melting point can satisfy the above-mentioned preferred melting point of the PP film. Moreover, the melt flow coefficient of 230 ° C (hereinafter referred to as MFR) When considering the extruding property or stretch processability when manufacturing 0 PP film, M 1 to 10 g / 10 min is better, and more preferably 3 to 6 g / 10 min. The polypropylene resin in Mingzhong does not hinder the effect of the present invention. Other resins can be mixed. There are no particular restrictions on the resins to be mixed. For example, there are polyolefin resins such as polyethylene and polybutene; polyolefin waxes; polyolefins Elastomers; hydrocarbon resins such as petroleum resins or terpene resins; copolymers of ethylene with vinyl acetate, acrylates, and acrylic monomers; or mixtures of these two polymers. As long as the above polypropylene resin does not impede the effects of the present invention, it can be combined with an antistatic agent, anti-capping agent, anti-adhesive agent, antioxidant, light stabilizer, crystallization nucleating agent, and smoothing agent as needed to provide smoothness Conventional additives such as surfactants for the purpose of anti-blocking and anti-adhesion properties. Printed clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, the thickness of the OPP film in the present invention is not particularly limited, and the preferred range is 5 to 10 wm In addition, the above 0 PP film may be a single-layer film or a multilayer film. A preferred form is, for example, a single-layer film with K propylene monopolymer as the main component, and M propylene Monomer-based layer and -8 of propylene and α-olefins other than propylene ~ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 490392 ——— Amendment A7 _.1 Fu Chong _, _B7_ — ......... ”V. Description of the Invention (7) Multilayer film with a layer of a random copolymer as the main component, etc. For the above-mentioned multilayer film, the thermal shrinkage rate and the like are considered, M The layer thickness of the propylene monopolymer as the main component is preferably 70% of the total layer thickness, and more preferably 80¾M. In addition, in the present invention, the OP film is considered suitable for packaging applications, especially when the gas barrier film is used, it is better to be transparent. Specifically, a haze value of M 15¾ M is preferable, and a more preferable value is 10% M. Π Ρ Ρ 隖 法 隖 Production method The OPP film with the above-mentioned thermal shrinkage rate used in the present invention can be used in the biaxial stretching method such as the tenter sequential biaxial stretching method and the tenter simultaneous biaxial stretching method as described below. It is manufactured by appropriately selecting post-processing conditions such as elongation processing conditions and thermal relaxation processing. For example, the stretching ratio is ten to two times in the tenter, and the MD direction is 3 to 5.5 times and the TD direction is 7 to 11 times. When the stretching ratio is less than 3 times in the MD direction and less than 7 times in the TS direction, the mechanical strength of the film (tensile elasticity, etc.) will not be reduced. However, when the MD direction is greater than 5.5 times and the TD direction is greater than 11 times, the thermal It is not desirable to increase the shrinkage rate. At this time, the stretching ratio when the tenter is extended in two axes at the same time is preferably 4 to 8 times in the MD direction and the TD direction at the same time. If the stretching ratio is less than 4 times, it is not desirable to reduce the mechanical strength of the film; if it is greater than 8 times, it is not desirable to increase the thermal shrinkage. The above-mentioned stretching processing conditions are extremely important to use temperature conditions that can control the orientation of the crystalline polypropylene-based resin, and generally, the stretching temperature is set at a relatively high temperature and M. -9 A paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) L .-- UV ------- Package -------- Order ------ --- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 490392 A7 ___B7___ V. Invention Description (8) (Please read the notes on the back to write this page) For example, The elongation temperature varies depending on the characteristics of the film-making machine. For example, when the tenter is successively biaxially stretched, MD stretching is usually performed by roller stretching. The heating temperature of the unstretched sheet during the roller stretching M 1 3 0 ~ 1 60 ° C is better, more preferably 140 ~ 155 ° C. When the heating temperature of the unstretched sheet when the MD is stretched is less than 130 ° C, it is not desirable to increase the thermal shrinkage, and if it is greater than 160¾, it is not required because the MD sheet will stick to the roller system. In addition, the TD stretching of the tenter by the two-axis stretching method is usually performed in the tenter. The heating temperature K 145 ~ 16510 during the tenter stretching is better, and the more preferable is 150 ~ 160C. If the heating temperature when the TD is stretched is less than 145¾, the thermal shrinkage becomes larger, which is not desirable. If it is more than 165¾, the film will be whitened instead of desirable. In addition, when the tenter is simultaneously extended in two axes, the heating temperature during extension is preferably 145 to 165¾, and more preferably 150 to 160 ° C. If the heating temperature during the stretching is less than 1 45 ° C, it is not desirable to increase the thermal shrinkage, and if it is higher than 165 ° C, the film will be whitened instead of desirable. After the above-mentioned extension processing, a heat treatment of about 1 to 8¾ in the MD direction and TD direction is performed for a few seconds to several tens of seconds in an atmosphere temperature of 160 to 18 °, as the OPP film can be made. It is preferred that the heat shrinkage rate be reduced to the desired range. When printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs using the above-mentioned highly crystalline PP 糸 resin as a film raw material, no special MD direction treatment is required as the above thermal relaxation treatment, and the above thermal relaxation treatment can be performed in the TD direction. The above-mentioned thermal shrinkage is achieved. The thermal relaxation treatment can be performed in-line after the T D stretching treatment. High score Poyang calendar (composite polymer calendar) -10- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 490392 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7 _; _ 5 Explanation of the invention (9) In the laminated film of the present invention, the polymer gas barrier layer of the laminated OPP film is a known one, and there is no particular limitation. For example, an oxide polymer obtained by subjecting a water-soluble polymer layer, a water-soluble polymer, and a metal alkoxide and / or a silane oxide to polycondensation by a sol-gel method is used. A composite polymer layer formed by condensing a water-soluble polymer and an oxide polymer. Among them, the composite polymer layer has superior gas barrier properties compared to a layer made of a water-soluble polymer alone, has a small temperature dependence of gas barrier properties, and is flammable and discardable for chlorine-based water-soluble polymers. Excellent, so it can be used in the present invention. The composite polymer layer is preferably a mixture of a partially hydrolyzed polycondensate and a water-soluble polymer of at least one alkoxide selected from a metal alkoxide and a silane oxide, and the part is hydrolyzed. A reaction product of a polycondensate and a water-soluble polymer or a mixture of the partially hydrolyzed polycondensate, a water-soluble polymer, and the reaction product. The above water-soluble polymer is a polymer which is completely dissolved or dispersible at normal temperature, and specific examples include polyethylene glycol and derivatives thereof; a polymer obtained by selecting a polyketone formed from a carbon monoxide-ethylene fluorene copolymer Alcohols; cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose; starches such as oxidized starch, etherified starch, dextrin; polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, or esters thereof , Salts and the copolymers of ethylene and the like; or polymers of these polymers modified by functional groups such as carboxyl, silyl, and the like. Among these water-soluble polymers, M polyethylene glycol polymer and its -11- (Please read the precautions on the back ^^ write this page first) »! Equipment (1¾¾ write female. J. paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 490392 A7 _B7_ V. Description of the invention (1Q) (Please read the notes on the back first to write this page) The derivative is better, and the degree of K saponification is 75 Molar % Polyethylene glycol on K, acetalized polyethylene glycol having a total hydroxyl group of 40 mol or less, the unit of ethylene glycol is 60 mol S; ethylene-ethylene glycol copolymer on Μ (hereinafter referred to as Μ Copolymerized polyethylene glycols such as ΕνΟΗ) and the like are more preferable. In addition, when considering the degree of polymerization of the above-mentioned polyethylene glycol-based polymers and their derivatives, when considering gas barrier properties or processability, ΙΟΟ〜5,000 is more preferable It is printed by 500 to 3,000. It is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, the metal alkoxide and silane oxide used in the formation of the composite polymer layer are polycondensed by the sol-gel method. There is no particular limitation on the formation of a metal oxide compound or a silicon oxide compound. Silane oxides that can form silicon oxide, such as methylsilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, etc .; tetramethyl Titanium alkoxides that can form titanium oxide such as titanium oxide, tetraethoxy titanium, methyl trimethoxy titanium, tetrabutoxy titanium, isoisopropoxy titanium, methyl triisopropoxy titanium, etc .; Tetramethoxyl, tetraethoxyl, tetrabutoxyzirconium, methyltrimethoxyl, methyltriethoxyzircon, methyltriethoxyl, methyltriisopropyl Oxyfluorene and the like can form oxidized zirconium oxides; trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, and methylisopropoxyaluminum can form alumina alkane oxidation Materials; magnesium alkoxides that can form magnesium oxide, such as tetramethoxymagnesium, tetraethoxymagnesium, tetraisopropoxymagnesium, etc .; glycidoxymethyltrimethoxysilane, 2-glycidoxy Ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltributoxysilane, (3,4-epoxycyclohexyl) methyl C-12-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 490392 A7 ___B7_ V. Description of the invention (11) Oxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, (Please read the notes on the back first to write this page) 3-(3,4-epoxycyclohexyl) propyltrimethoxysilane and other silane oxides with epoxy groups; amines Methylmethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 1-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethyl Oxysilane, N-aminomethylaminomethyltrimethoxysilane, H-aminomethyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and other silane-containing silane oxides; vinyltrimethoxysilane, Vinyl triethoxysilane, N-yS-U-vinyl benzylaminoethyl-aminopropyltrimethoxysilane or its hydrochloride-containing silane oxide; and These metal alkoxides or silane oxides One or two types of alkoxy compounds substituted with halogen atoms in the compounds. One or two mixtures on the M. 0 The Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives printed on the above metal alkoxides and silane oxides. There are tetramethoxysilane, tetraethoxysilane, tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium, tetraisopropoxytitanium, tetramethoxyzirconium, tetraethoxyzirconium, Tetrabutoxyzirconium, trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylbutoxysilane. The composition for forming a composite polymer layer in the present invention can be prepared by appropriately selecting the above-mentioned water-soluble polymer and the above-mentioned metal alkoxide and / or silane oxide and mixing them. At this time, the above water-soluble polymers and the above 13- this paper size are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 490392 A7 _B7___ 12 V. Description of the invention () (Please read the precautions on the back first (Write this page) 混合 The mixing ratio of rhenium metal alkoxides and / or silane oxides is based on the proportion of water-soluble polymers and oxidized metal compounds and / or silane oxides in the composite polymer formed in the laminated film (water-soluble The ratio of polymer / oxide metal compound and / or silane oxide wU / wt%) is 10/90 to 80/20, which is determined by M. Since it can exhibit good gas barrier properties, it is desirable. When the above-mentioned ratio in the composite polymer is considered in terms of gas barrier properties and humidity dependence, M20 / 80 to 70/30 is more preferable. In the laminated film of the present invention, the thickness of the polymer gas barrier layer is not particularly limited, but when considering the gas barrier property of the laminated film, M 0. 1 // m is preferable, and more preferably 0.3 / imK. When considering the economy and the secondary processability of the effect of the laminated film, etc., it is better at M 10 w mM, and more preferably it is 6 // mK. High score for yang yang, calendar (composite polymer eve formation method) In the method for manufacturing the laminated film of the present invention, the formation method of the polymer gas barrier layer is not specially made, and a conventional formation method can be adopted. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For example, the formation of a composite polymer layer is generally coated on at least one OPP film with a specific heat shrinkage ratio as described above, which is composed of water-soluble polymers and metal alkoxides and / or A coating liquid made of a composition of a silane oxide is a method in which a metal alkoxide and / or a silane oxide is polycondensed by a sol-gel method, and then dried and hardened. The composition of the coating liquid is not particularly limited as long as the polycondensate of the metal alkoxide and / or silane oxide can be formed on the surface of the OPP film until it is dried and hardened. For example, the water-soluble polymer and aurantane oxide and / or silane oxide are uniformly dissolved or dispersed in -14- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) Intellectual property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 490392 A7 _B7_____ 1 7 V. Description of the Invention () Composition of liquid substance in solvent, or composition with hydrolytic agent, or metal alkoxide and / Or silane oxide, if necessary, add a water-decomposing agent, and prepare the oxide polymer as a polycondensate beforehand, and then dissolve or disperse it in the solvent uniformly with the water-soluble polymer. The above-mentioned hydrolytic agent is a conventional substance and is not particularly limited. Specifically, for example, an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid, or an alkali aqueous solution such as sodium argon oxide, ammonium, or an organic amine compound can be used as a hydrolytic agent only by water to M. In the above-mentioned coating liquid coating method, in the practice of the present invention, a solution or a solvent dispersion coating method that can coat the film at a high speed is preferably used. Specific examples of this coating method include coating the coating liquid by gravure, reversible coating, spray coating, contact coating, mold coating, main ring rod coating, chamber-blade and gravure coating. It is advisable to cover the surface of the OPP film with a low-cost coating. The solvent for dissolving or dispersing the water-soluble polymer is preferably M water or a water / lower alcohol mixed solvent. Among them, in the case of Kao adhesiveness and productivity, it is better to use a water / lower alcohol mixed solvent. The lower alcohol is preferably an alcohol having 1 to 3 carbon atoms, and specific examples include methanol, ethanol, n-propanol, and isopropanol. The mixing ratio of water / alcohol M is appropriately selected within a range of 99/1 to 20/80. In addition, when the above coating solution is used to improve the coating suitability of the OPP film, other water-soluble organic compounds may be added within a range that does not hinder the stability of the coating solution. Specifically, the paper used for solvent removal is -15- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -L --- ^ ---, ---- install- -(Please read the notes on the back to write this page). 490392 A7 B7__ ^ 14 V. Description of the invention () (Please read the notes on the back to write this page) In addition to the lower alcohols mentioned, for example, ethylene glycol, propylene glycol And other alcohols; alcohol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; polyhydric alcohols such as glycerol and fluorene; ethers such as dioxane and trioxane; acetic acid Esters such as ethyl esters; Ketones such as methyl ethyl ketone; Water-based tackifiers for water-based isocyanates, polyethyleneimines, and epoxy resins. In the method for manufacturing a laminated film of the present invention, the method for drying the coating film of the OPP film is a conventional drying method, and is not particularly limited. Specifically, for example, one or two kinds of M upper heat roller contact methods, heat medium (air, oil, etc.) contact methods, infrared heating methods, microwave heating methods, and the like are used. Among these, a heated air contact method or an infrared heating method is preferred in terms of processing and drying efficiency of the appearance and the like of the Khao film. Especially when drying the above-mentioned composite polymer layer, when considering gas barrier properties or drying efficiency, it is preferable to use a temperature of 100 ° CK in a temperature range lower than the melting point of the base film. The preferred lower temperature is 110¾, especially 120¾. Moreover, the preferred upper temperature is a temperature lower than the melting point of the substrate film, especially a temperature lower than 15 £. When the above-mentioned drying time is considered in consideration of gas-barrier property and drying efficiency, M 5 seconds to 10 minutes is preferable, and 10 seconds to 5 minutes is more preferable. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and before and after the above-mentioned drying, it can be irradiated with high-energy rays such as ultraviolet rays, X-rays, electronic rays, etc., as required, in combination with components polymerized by high-energy irradiation It is advisable for M to irradiate this high energy line. When the above-mentioned polymer gas barrier layer is a composite polymer layer, a method for forming the same will be described, and the method is carried out by a method of forming a water-soluble europium molecular layer or a conventional method, and is not particularly limited. Generally speaking, it is prepared to dissolve water in the above-mentioned solvents. The paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) 490392 A7 _B7 _ ^ _

1 R V. Description of the invention () A method for coating a soluble polymer and making it the basis of the above coating method. (Please read the note on the back to write this page first) Modification of 0PP thin meal The preferred form of the present invention is to improve the adhesion to the OPP film of the composite polymer layer, and to further improve the obtained laminated film. For gas barrier properties and durability, the above-mentioned OP film is applied to a laminated film of various surface finishers. In other words, a preferred form of the present invention is to provide a laminated film having a surface of an OPP film laminated with a polymer gas barrier layer and subjected to a corona discharge treatment and / or a flame treatment such as a flame under a nitrogen and / or carbon dioxide atmosphere. The surface of the 0PP film on the side of the polymer gas barrier layer is subjected to a corona discharge treatment and / or a flame treatment such as a flame under a nitrogen and / or carbon dioxide atmosphere, and a layer with a thickened coating is formed on the surface. film. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. (3) The PP film on the side of the laminated polymer gas barrier layer has at least one selected from the group consisting of acid-modified polyolefin, ethylene-containing polyolefin, and butene-1- After a layer of polyolefins formed by a group of polyolefins, the surface of the layer is subjected to a corona discharge treatment and / or a plasma treatment such as a flame under a nitrogen and / or carbon dioxide atmosphere. In the above-mentioned laminated film, the corona discharge treatment applied to the OPP film must be performed in a nitrogen and / or carbonic acid atmosphere. When considering the economy, the M nitrogen atmosphere is preferred. In addition, the oxygen concentration in the atmosphere of nitrogen and / or carbonic acid gas is taken into consideration. -17-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 490392

Year 13 · ^ 'Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 V. Description of the invention () ο When the adhesion between the PP film and the composite polymer layer, 5 capacity S; better under Μ, better The capacity is 3: ί: Κ 下. The corona discharge treatment density M5 to 100W · min / m2, which is calculated from the voltage X current / (electrode width X film travel speed) (W · m i η / m2), more preferably 10 to 70W · min / m2. In other words, when the treatment density of the surface of the OPP film is less than 5W · min / m2, it is not desirable to reduce the adhesion, and if it is greater than 100W · in i η / in 2, there will be a gap between the PP films. Adhesion is generated, and the treatment of the spots in the width direction of the film is different, and it is not desirable. The wetness index of the treated surface of the 0 PP film after the above corona discharge treatment is preferably 40 to 55 mN / ro, and more preferably 45 to 50 mN / in. When the wetting index is less than 40mN / m, it is not desirable to reduce the adhesiveness, and if it is greater than 55mN / m, adhesion between 0PP films will occur, and the treatment degree will be different for the width direction of the film. . This treatment spot is not desirable because of the cause of the coating spot or the adhesion strength spot at the time of coating. In addition, in the above-mentioned plutonium laminated film, the flame plasma treatment is a plasma ionized in a flame generated when a flammable gas such as natural gas, LPG, propane gas, butane gas is burned by a burner. Blow on the surface of OPP film. In this flame plasma treatment, the treatment intensity by the flame plasma is different depending on the OPP film processed, but M is appropriately selected from 1 to 15 kcal / m2, and more preferably 2 to 10 kca 1 / m 2. In other words, if the processing strength is less than lkcal / m 2, the reduction in adhesion with the sol-gel composite polymer layer is not a goal, but if it is greater than 1 5 -1 8-this paper size applies the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) t — # ------- install -------- order ------- (please read the precautions on the back before filling this page) 490392 A7 B7_V. Description of the invention (17) At kcal / m2, the OPP film will wrinkle due to heat shrinkage, etc., or the end portion will become thicker due to heat shrinkage due to poor cooling (M below (It is called the standing ear phenomenon). The above treatment intensity is the energy of the flame, the walking speed of the film (m / min), and the width of the film (m η) and the burning output (kcal / m · min) of the unit burner length (m). m). The length of the burner (the same length as the width of the film) (m) used in the film processing is calculated by the following formula (i). (Please read the notes on the back first to write this page) | 黼 _ I! Loader burner output (kcal / m · min) X Burner length used in processing (m) Processing intensity = -⑴ (kca 1 / m 2) Film width (m) x film walking speed (m / min) Printed by the above-mentioned flame plasma treatment by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, from the front end of the flame to the surface of the film on the object to be treated When considering the stability of the distance and the like, the distance is preferably 1 to 5 mm, and more preferably 1 to 3 mm. In addition, the flame plasma treatment is generally a method in which a flame plasma is blown while the film M is in contact with a cooling roller on one side of the film and the film is walking on the other side of the film. At this time, the temperature of the cooling roller is appropriately selected from the range of room temperature to 601, and preferably 30 to 451C. The wetting index M 3 5 ~ 65mN / m of the above-mentioned flame plasma treated 0 Ρ Ρ film treated surface is better, more preferably 40 ~ 60mN / m, and most preferably 45 ~ 60 mN / m ° -1 9 One paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 490392

Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (18) If the wetness index is less than 35mN / m, the decrease in adhesion with the sol-gel composite polymer layer is not a goal, but if When it is larger than 65 m N / m, wrinkles may occur due to the thermal shrinkage of the film, or adhesion between the base film may not be desirable. The surface thickness (K a) of the treated surface of the 0 PP film treated by flame plasma treatment, when considering the adhesiveness, M 0 .5 ~ M) nm is better, more preferably 1 ~ 80 nm, and the best is 2 ~ 50nm. The above-mentioned corona discharge treatment and flame plasma treatment may be performed separately on the surface of the 0 P P film, or may be used in combination. The treatment sequence M is finally applied to the flame plasma treatment. In addition, the surface treatment of the OPP film used in the present invention may be combined with a surface treatment other than the above-mentioned treatment, as long as the effect of the present invention is not impaired. Specifically, for example, a plasma treatment for energizing an inert gas, an electron beam irradiation treatment, an ultraviolet irradiation treatment, and the like. By forming the composite polymer layer on the treated surface to which the above-mentioned treatment is applied, the preferable laminated film of the present invention having excellent gas barrier properties and durability can be obtained. The formation of the above-mentioned laminated film in the case of the hydrophobic inspection is because the adhesion-promoting coating layer is laminated on the treatment surface of the 0 PP film applied with the above-mentioned corona discharge treatment and / or flame plasma treatment, so as to further improve it. The adhesion strength of the formed composite polymer layer is stable and the laminated film is stable. The thickening coating agent used for forming the thickening coating layer is a conventional material and is not particularly limited. For example, isochloride, polyurethane 糸,-20- (Please read the precautions on the back before filling this page) -ir · Binding-binding ---------- This paper size applies China National Standard (CNS) A4 specification (2) 0 X 297 mm) 490392 A7 B7__ 1 q V. Description of the invention () Polyester, polyvinylimide, polybutadiene, polyolefin, alkane Tackifier coatings based on phthalic acid esters. Among these, when considering the effect of the present invention, an isofluoroester-based, polyurethane-based, or polyester-based tackifying coating agent is preferred, and one or two types are more preferred. Isofluorate compounds, mixtures of polyurethanes and urethane prepolymers and reaction products, mixtures of one or two polyesters, polyalcohols, polyethers, and isofluorates and reactions Products, or these solutions or dispersions. The method for laminating a tackifying coating layer on the treated surface of the above-mentioned biaxially stretched polypropylene film treated with flame plasma is not particularly limited. In the industrial implementation, the coating liquid of the above tackifying coating agent is borrowed. The method of applying κ lamination by gravure coating, reversible coating, spray coating, contact coating, mold coating, metal ring coating, chamber doctor blade, and photogravure coating is preferred. . In addition, the amount of the tackifying coating layer is preferably 0.01 to 5 g / m 2 in dry weight, and more preferably 0.1 to 2 g / m 2 in dry weight. By forming the composite polymer layer on the treated surface to which the above-mentioned treatment is applied by the above-mentioned method, the laminated film of the present invention having excellent gas barrier properties and durability can be obtained.

The Bg modified polyolefin is formed into the laminated film of the above (3) by forming an acid-modified polyolefin layer on the surface of the OP film and subjecting its surface to the above-mentioned corona discharge treatment and / or flame plasma treatment. In order to improve the adhesion strength of the composite polymer layer formed thereon, and a stable laminated film. For the resin constituting the above-mentioned acid-modified polyolefin layer, in consideration of adhesion and the like, the total amount of monomers containing unsaturated organic acid anhydrides in the total amount of M is 0.01 ~ -21- This paper applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) (Please read the notes on the back to write this page first) »! Printed by the Consumers 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 490392 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed A7 B7__ 2 0 DESCRIPTION OF THE INVENTION () 15 weight SS, more preferably 0.1 to 10 weight%. The acid-modified polyolefin resin may be used alone or as a mixture of the acid-modified polyolefin resin and the polyolefin resin. If the monomer unit of the unsaturated organic acid anhydride is less than 0.01% by weight, it is not desirable to reduce the adhesion, and if it is more than 10% by weight, the transparency is not desirable. The above-mentioned acid-modified polyolefin resin 僳 is a polyolefin modified by copolymerizing or grafting an unsaturated organic acid anhydride shown in the above 酸, or an unsaturated organic acid anhydride and a derivative thereof. Specific examples include unsaturated organic acid anhydrides, or modified with unsaturated organic acid anhydrides and derivatives thereof, acid-modified polypropylene, acid-modified polyethylene, acid-modified ethylene-propylene copolymer, acid-modified ethylene-vinyl acetate copolymerization Materials, acid-modified ethylene-butene copolymers, acid-modified propylene-butene copolymers, and the like. Among these, in consideration of transparency, heat resistance, etc., it is preferable to use unsaturated organic acid anhydrides, or to modify unsaturated acid anhydrides and derivatives thereof, and to modify the acid-modified polypropylene. There is no particular limitation on the M F R of the acid-modified polyolefin resin, and when considering the polar groups, processability, etc. that migrate to the surface, 0.1 to 150 g / lOroin is preferable, and 5 to 1 GOg / lOmin is more preferable. Specific examples of the unsaturated organic acid anhydride include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid. Further, an acid anhydride derivative obtained by using the above-mentioned acid anhydride with a diol, amino alcohol, diamine, or the like can be used in combination. The aforementioned diols, amino alcohols, diamines, and the like are not particularly limited, and examples thereof include glycols such as ethylene glycol and propylene glycol, amino alcohols such as amino ethanol, amino butanol, ethylene diamine, and diamine groups. Diamines such as butane. In the acid-modified polyolefin layer used in the present invention, the polyolefin resin mixed with the above-mentioned acid-modified polyolefin resin is polypropylene, polyethylene, and ethylene-(Please read the precautions on the back to write this page) i: Binding · _-Line "This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 490392 A7 B7 2 1 V. Description of the invention () Polyolefins such as α-olefin copolymers, etc., there is no special When considering transparency, heat resistance, etc., the ethylene-propylene random copolymer is composed of polypropylene propylene monomer, ethylene-containing monomer, and the unit is 0.1-15 mol%. 1. The ethylene-propylene-1-butene random copolymer containing 1 to 15 mol% of monopolymer units containing ethylene and butylene is preferred. The MFR of the above-mentioned polyolefin resin is preferably 0.1 to 20 g / 10roiii in consideration of extrusion processability, and more preferably 1 to the thickness composition ratio of the above-mentioned acid-modified polyolefin layer. There is no particular limitation on adhesion. In terms of performance, processability, cost, etc., 1 to 5fl% is preferable, and 5 to 30% is more preferable. Moreover, in the laminated film of the above (3), the electric discharge treatment and / or flame treatment performed on the acid-modified poly (fluorene) fluorene layer is performed under the conditions detailed in the above-mentioned laminated film, and after the electric discharge treatment The wetness index of the treated surface is 40 ~ 55ffN / m, preferably 45 ~ 50roN / m. By forming the composite polymer layer on the treated surface to which the above-mentioned treatment has been applied, the laminated film of the present invention having more excellent gas barrier properties and durability can be obtained.籀 靥 Thin 臌: > Change temporarily (Three 靥) The laminated film of the present invention, and by laminating an arbitrary thermoplastic resin film on the surface of the composite polymer layer, can provide various functions in addition to the effect of the present invention Laminated film. In other words, the present invention does not provide a laminated film formed by laminating a thermoplastic resin film on a surface having a high molecular gas barrier layer on one side of a 0 P P film having a thermal shrinkage of 5% or less. In this laminated film, the thermoplastic resin of the raw material resin of the thermoplastic resin film, such as olefin strip resin of polyethylene, polypropylene, etc., -23- This paper size applies to China National Standard (CNS) A4 (210 X 297) (Mm) 丨 * --- ten ---: ---- ^ install --- (please read the notes on the back to write this page first) · --- line _ printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7___ 2 25. Description of the invention () Polyester strips of polyethylene terephthalate, polybutylene terephthalate, polyethylene-2, 6-naphthoate, etc. Resin, Polyamide resins such as Nylon 6, Nylon 12, etc., polyvinyl chloride, ethylene vinyl acetate copolymer or saponified, polystyrene, polyetherester, polycode, polyoxyphenylene , Polyphenylene sulfide, aromatic polyimide, polyimide, polyimide, polyacrylonitrile, polyethylene glycol, etc., and copolymers thereof. In addition to the above-mentioned gas barrier function, the laminated film according to the present invention is preferably used for the purpose of preventing the problem of poor thermal plates caused by the contents adhering to the packaging material. That is, the surface specific resistance of the laminated film is adjusted so that the surface specific resistance of the film surface of the sheet surface 10 g Ω is 11 or less. In other words, the present invention does not provide a laminated film formed by laminating a polymer gas barrier layer on at least one side of an OPP film having a thermal shrinkage of 5¾ or less, and having a surface intrinsic resistance logQ of 11 or less on at least one side. The laminated film of the present invention allows the surface having a charge preventing property to be formed by a conventional method for preventing a charge. For example, a method of applying a charge preventive agent to the surface of a laminated film, a method of blending a charge preventive agent with a raw material resin of the film, and the like. When used as a conventional antistatic agent, the compatibility of the resin with the resin, thermal stability, physical properties, environmental suitability, low cost, etc. are appropriately selected, and one or two or more thereof are appropriately selected. Specific examples of the antistatic agent include fatty acid esters of polyhydric alcohols such as glycerol fatty acid esters, sorbitol fatty acid esters, pentaerythritol fatty acid esters, polyethylene glycol fatty acid esters, and polyglycerol fatty acid esters Antistatic agent, alkyldiethanolamine, alkyldiethylolamine fatty acid esters and other alkylamine strip antistatic agents, diethanolamine and fatty acid alkyl diethanolamineamine antistatic agent, trialkylbenzene Methylammonium salts, tetraalkylammonium salts, and other cationic charge prevention agents, -24- (Please read the precautions on the back to write this page) Binding.-丨, This paper size applies to Chinese National Standards (CNS) A4 size (210 X 297 mm) 490392 A7 B7

23. V. Description of the invention (Amphoterics such as alkylbenzene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, etc., anionic charging inhibitors, alkyl betaines, alkyl oxazolines, etc. Ion-based antistatic agent. Among these are Kaul antistatic properties, adhesion, etc., with one or two or more glycerol fatty acid esters, sorbitol fatty acid esters, alkyldiethanolamine, and alkyldiamine. Ethanolamine fatty acid esters and alkyldiethanolamines are preferred as antistatic agents. In addition, the number of alkyl carbons of the above fatty acids and alkylamines is preferably 6 to 2 when the antistatic property is considered, and more preferably 1 2 to 2 0. In the formation of the above-mentioned laminated film, the optimum form is a form of a thermoplastic resin film having a surface inherent logQ of 11 M on a polymer gas barrier layer. A specific layer structure is, for example, high. 0PP film with molecular gas barrier history / surface specific resistance ΙεεΩ of 11 or less, thermoplastic resin film / polymer gas barrier layer / 0PP film with surface intrinsic logQ of 11M, 0PP film with surface inherent resistance 10g2 of 11 or less / Polymer gas barrier layer / Surface solid Thermoplastic resin film with a resistance logQ of 11 or less. Among these, in order to prevent the contents of food packaging from adhering to static electricity and used in bag packaging applications, the inherent resistance on the K surface is 10 g Ω, a thermoplastic resin of 11 or less The film is preferably in the form of a sealing film. The thickness M 5˜100 0 // in of the above thermoplastic resin film is preferable, and the thickness is more preferably 10˜80 // π. The application of the laminated film of the present invention is not particularly limited, M gas barrier (oxygen barrier, nitrogen barrier, carbon dioxide barrier, etc.) films are suitable for food packaging films, especially for water food packaging, heating, distillation-25-This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 mm) ----- V ------- install -------- order --------- ^ 9. (Please read the back first (Please note this page before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 490392

7 7 A B /·.0 a 月 .1 Αyear 9 HQ-v 2 4. L --- 5. Description of the invention () Screening of sterilization treatment packaging film. There are no particular restrictions on the packaged items, for example, pickles, miso, miso, fish plate, tubular fish paste, aquatic processed products, burgers, hot dogs, Wiener sausages, ham, other processed meat products, cheese, cream, hemp Rice dumplings, yam juice konbu, curry, stewed wonton food, bagged rice, etc. In addition, it can also be used in industrial packaging applications such as pesticides, medicines, fertilizers, precision materials, medical, electronics, chemistry, and maple. Examples The present invention will be described in the following examples and comparative examples, but the present invention is not limited to these examples. The properties of the resins and films of the following examples and comparative examples were measured by the following methods.测定 Determine the main peak scale by DSC of the raw resin. Take about 5 ~ 6mg of sample, seal it in an aluminum pan, and use a differential calorimeter to increase the temperature from room temperature to 235 ° C in a nitrogen gas flow of 20ml / min. Hold for 10 minutes and then cool to room temperature at 10 ° C / mi. Then, the main peak was measured at a melting curve obtained at a heating rate of 1Q ° C / min.测定 Measure the main peak by DSC of the thin film. Take about 5 ~ 6 mg of the sample by weighing, seal it in an aluminum pan, and use a differential calorimeter in a nitrogen gas flow of 20ml / min at a heating rate of 10 ° C / roin. The melting curve was raised to 2 3 5 ° C to determine the main peak.

(3) MFR is measured based on J I S K 7 2 1 G. ⑷Wulian Fraction (mmiiiin value) and copolymerization composition-26- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page)-Install ---- s'. Printed clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 490392 A7 B7 2 5 V. Description of the invention (using Japanese electronics JNM-GSX- 2 7 0 (13 C-NMR frequency 6 7. 8 Μ Η 2) Measured under the following three conditions. Measurement type Fluctuations Wide fluctuation Repeat time Accumulation times Solvent sample concentration Measurement temperature (Please read the precautions on the back before filling this page) 1 Η-Completely decoupled 7 · G microns ( C4 5 degrees) 3,0,0 0 times, mixed solvent of original dichlorobenzene / heavy benzene (90/10% by volume)

120 m g / 2.5 m 1 solvent 1 2 0 ° C At this time, the minnim pentad fraction 傺 was determined by measuring the split peak in the methyl range of the 13 C-NMR spectrum. Moreover, the assignment of the peaks in the methyl range was performed according to A. Zambelli et al [Macromolecules 13, 267 (1980)]. The haze (H a z e) is measured based on JI S K67 14. ⑹Heat shrinkage rate The heat shrinkage rate in the M D direction and the T D direction at 150 ° C was measured according to J I S C 2 3 1 8 as a reference. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. 气 Gas barrier properties were measured using an oxygen transmission rate measuring device (produced by Roocon Corporation; OX-TRAN100) based on JIS K7 12 6 B method. Measurement conditions 僳 The measurement was performed in an atmosphere of 25 ° C, 05UH, 80% RH, and 90: UH. ⑻Moisture resistance (water vapor resistance) Based on JISK 7 1 2 9 B method, using a moisture permeability measuring device 27- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 490392 A7 B7 V. Description of the invention (2 6. Under 40 υ, 90% (manufactured by Mocon Corporation; PERMATRAN-W TWIN), RH atmosphere. 薄膜 The appearance of the film after the coating process is a biaxially stretched polypropylene film with a width of 30 cm The appearance of the film after coating and drying and hardening under the following conditions is evaluated according to the following criteria. (Conditions) Guide roll bow type hot air jet nozzle blown rod coating machine method 18 m / mi η 6 m 1 00 ~ 140C 20 seconds Printed drying method for employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs: Coating method: Coating speed: Drying furnace length: Setting temperature: Drying time:. (film appearance evaluation) ◎: No folds at all 〇: Slight wrinkle X: Corrosion discharge treatment is quite visible. Corona discharge treatment tester made by Kasuga Electric Co., Ltd. was used. K Surface treatment was performed under the following conditions. Under the atmosphere Corona discharge treatment. Introduced gas: nitrogen or nitrogen / carbonic acid gas. Oxygen concentration: film walking speed at 5 capacity M: 100 in / mi η electrode: alumina type 3 electrode coiling situation. Coiling situation. Coiling The paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the notes on the back to write this page) 490392 A7 B7% 4ηή ^ ί 5. Description of the invention (2 7, I ί · '.1-Distance between films: 2. Omm Machine: AGI-200 manufactured by Kasuga Electric Corporation

Front roll temperature: 6 5 ° C Processing width: 15000mm 7 Flame plasma treatment Flame plasma treatment by Brin, Burner (company) (USA) Flame plasma treatment test Surface treatment was performed under the following conditions. : Natural gas (air mixing) device output: 328 ~ 853kcal / m · min (combustion Carrolly with burner width 1 m, 1 in 丨 η) distance between inner flame and film surface: 2mm walking speed: 100m / min roller Temperature: 3 8 υ Processing width: 600mm Printed electrodes produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs are effective in processing electrodes (11) Fire machine, fuel cannon film is burned. Cooling is effective (12) Viscosity 2 in a full atmosphere评估 Evaluate the cracks between some of the samples (please read the precautions on the back before filling this page). The surface treatment surface of the substrate film (12X 12cm) overlaps with the reverse surface under a load of 10 kg at 50 ° C. Humidity 90% R Η 24 hours. Cut out 30mm wide and 40mm long wrapping materials with cracks and cracks (one film on each of the upper and lower grids), and use a tensile tester (tensile speed: 100mm / m ί η, A distance of 40 mm) was used to measure the shear peel strength. 29-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 490392 A7 B7 V. Description of the invention (2 8. Evaluation of shear peel strength U / cm 2 Employee Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Printed ◎ 〇X (13) The surface of the probe is scanned by several times using a needle microscope. The probe is half-probe material. Scanning speed calculation standard calculation standard calculation standard (1 4). The central part κ degree is as follows 5: X cut 10 W 10 ~ 30Κ thickness (R a) Citaruin history Η (Nano S c ο p 1) The common covering machine sets the amplitude of the frequency of the fixed-cycle vibration at 30 points below the base section of the X-cut for 1 day.

Scanning probe a) manufactured by Lumpitz (transliteration) a), Measured under the following conditions, based on the surface thickness of the core wire. Tapi Valley (transliteration) type AFM 100 / i mX 10 u m 5 ～ 1 0 n m single crystal silicon 1.5 Η z 1.5V

1.1- 1.3V

3 00KH -L --- TIT ---- (Please read the notes on the back first to write this page).-| Line_ Biaxial extension is about K and the tape method grants M to the surface of the polypropylene film without peeling. Manually apply 3wm of coating solution and dry. The coating surface of the obtained laminated film (J IS K5 400) was used as a reference, and the peeling was evaluated. Scenario -30- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 490392 A7 B7 .mn, -4 Dazheng a- V. Description of the invention (2 9 Supplemental nuclear resonance frequency 6 7. 8 The X-cut part has a peeling condition of 1 部份 or less. The X-cut part has a peeling condition of 1 to 3 S: The peeling condition of the X-cut part is 3 to 5% and the peeling condition of the X-cut portion is 5 to 10. :!: Peeling condition 〇: X-cut part has 10% peeling condition (1 5) Sealing strength: Use a 5X20 Gmin heat sealing rod between the laminated film sealant surface and heat seal at 150 ° C. Under the conditions of heat-sealing pressure of 1 kg / cm2 and heat-sealing time of 1.0 second, a 15-inch-inch wide sample was cut from the sealed sample, and a tensile tester was used, the tensile speed was 1 mm / min, and the sample length was 40 mm. (Inter-lattice) was used to measure the tensile strength as the seal strength. The result 傺 is the average value of 5 samples. (1 6) Pentascore (mminin value) and copolymer composition use JNM-GSXITtM13 MH Η z), measured under the following conditions. Measurement type: 1Η- Complete decoupling Wave width: 7 · 0 micron (C 4 5 degrees) Accumulation times: 1 G, G 0 0 times Solvent: Original dichlorobenzene / heavy benzene mixed solvent (9 0/1 0 volume

5U sample concentration: 120 mg / 2.5 m 1 solvent

Measurement temperature: 1 2 0 ° C At this time, the mm mm pentavalent fraction (by measuring the methyl range of the CN CN MR spectrum 3 1) This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) L --- ^ ------- Equipment -------- Order --------- (Please read the precautions on the back before filling out this page) Staff of Intellectual Property Bureau, Ministry of Economic Affairs Consumption cooperative prints 490392 9iyi -6 amendment 丨

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs π 2 5 V. Description of the invention () The split peaks around M were obtained by M. Moreover, the assignment of peaks in the methyl range was performed according to A. Zambelli et al [Macromolecules 13, 267 (1980)]. Haze (Haze) Example 1 The resin A shown in Table 1 was extruded into a sheet shape under heating and melting at 2800 ° C using a T-shaped mold extruder, and was cooled and hardened on a chill roll. After that, it is stretched 4.4 times at a sheet temperature of 1 5 1 ^ by a heating roller stretcher, and then stretched by 10. 5 times at 15.8 ° C by a tenter cross stretcher. In the atmosphere temperature of 175 ° C, heat curing for 10 seconds, and 8% relaxation treatment in the TD direction, to obtain a two-elongation polypropylene film. Corona treatment was applied to one side of the obtained biaxially stretched polypropylene film. The evaluation results of the obtained biaxially stretched film are shown in Table 2. Then, 30 parts by weight of tetraethoxysilane, 20 parts by weight of ethanol, 1 part by weight of 2 N hydrochloric acid, and 4 parts by weight of water were mixed and stirred at room temperature for 1 hour. Then add 3 parts by weight of 7_glycidoxytrimethoxysilane, 40 parts by weight of Soarolu (transliteration) 20L (Ethylene-ethylene glycol water / IPA solution manufactured by Japan Synthetic Chemical Co., Ltd.), 0.15 parts by weight of N, N-dimethyl benzylamine was mixed with M to prepare coating solution A. On the corona-treated surface of the above-mentioned biaxially stretched polypropylene film, the above-mentioned coating solution A was applied by a rod coater, and the thickness of the coating layer after drying was 3 / im, and dried and hardened under the conditions shown in Table 3. . The evaluation results of the obtained laminated film are shown in Table 3. Examples 2 and 3 and Comparative Examples 1 and 2 except that the biaxially-stretched polypropylene film shown in Table 2 is used, and M Table 3 -32-This paper size is applicable to China National Standard (CNS) A4 (210 X 297) Li) ----- r ------- install -------- order · -------- (Please read the precautions on the back before filling this page) 490392

7 7 AB .y Years i side | Xiu ii Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (31) except that the pieces are dried and hardened, the same operation as in Example 1 is performed to obtain a laminate film. The evaluation results are shown in Table 3. Comparative Example 3 A laminated film was produced in the same manner as in Example 1 except that Soaroru 20L monomer was used as a coating agent. The evaluation results are shown in Table 3. Table 1 Resin copolymer composition Mohr% MFR g / 10min DSC peak apex ° C Pentalink additive anti-adhesive part by weight A propylene monomer-4 165 0,985 M; 0.05 B propylene-ethylene random copolymer ; 0.2 3.2 163 0.973 M; 0. 05 C propylene-ethylene random copolymer ethylene; 0.5 3, 5 158 0.930 M; 0. 05 D propylene-ethylene random copolymer ethylene; 4 7 138-M; 0.05 Μ: Spherical melamine resin particles (average particle size 1.5 // ro) -33- only, paper size applies Chinese National Standard (CNS) A4 specifications (21〇 29.7. Mm) if nn · I · ϋ nv ϋ nnn · Yikou, I · ϋ ni— ϋ (Please read the precautions on the back before filling in this page) 490392 A7 B7 One U—_ t., W / wi. 5. Description of the invention (#) Table 2 Types of raw resin DSC wave peak apex film ° C thickness um thermal shrinkage MD / TD% haze% corona treated surface wetness index mN / ma A 175 20 2.5 / 2.0 2 40 b B 168 20 3.5 / 2.3 2 42 c C 163 20 6 / 8 3 42 Table 3 Dry-hardening conditions of printed substrate films printed by employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs, oxygen barrier o% m / mm cc / m 2 · day · atm Water vapor g / m 2 · day · atm Appearance Example 1 a 141 ° C 2 minutes 2/3 3 · 8 〇 Example 2 a 131 ° C 2 minutes 3/4 4.2 ◎ Example 3 b 136¾ 2 points 3 / 4 5 〇 Comparative Example 1 c 951 2 points 5/15 5.5 〇 Comparative Example 2 c 131 ″ 2 points 4/6 5.5 X Comparative Example 3 a 1411 2 points 3/15 4 · 4 〇-34- l · — ^ ------- Installation -------- Order --------- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 Specifications (210 χ 297 mm) 490392 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7_ V. Description of Invention () 33 Example 4 The resin A shown in Table 1 was extruded with a T-shaped mold. 8 0 t, extruded into a sheet-like shape under heating and melting, and cooled and hardened on a cold hard roll, and then stretched by a heated roll stretcher at a sheet temperature of 148¾ and stretched 4.4 times in a longitudinal direction, and then transversely by a tenter The stretcher was stretched 9.5 times at 163 ° C, and then heat-hardened for 10 seconds at an atmosphere temperature of 168 ^, and subjected to 8% relaxation treatment in the TD direction to obtain a biaxially stretched polypropylene film. Then, flame plasma treatment (treatment intensity: 6.5 kcal / m2) was performed on one surface of the film to obtain a surface-treated substrate film of 20 wm. The evaluation results of the obtained surface-treated substrate film are shown in Table 4. Then, on the surface-treated surface of the obtained surface-treated substrate film, the coating liquid A obtained in Example 1 was applied by a rod coater. After drying, the thickness of the coating layer was 3 wm, and it was dried and hardened at 1201C for 2 minutes. . The evaluation results of the obtained laminated film are shown in Table 5. Examples 5 and 6 A laminated film was obtained in the same manner as in Example 1 except that the surface-treated substrate film shown in Table 4 was used. The evaluation results are shown in Table 5. Example 7 On the composite polymer layer of the laminated film obtained in Example 4, a tack coater was applied using a rod coater (TM 3 29 / CAT-8B manufactured by Toyo Morton Co., Ltd. 100 parts by weight / 100 Parts by weight are adjusted to a non-volatile content of 10% by weight in an ethyl acetate solvent. After drying, the dry weight is 2 g / m 2 and then dried at 80 t. In addition, dry lamination of 40 / im without extension on the above-mentioned thickened coating layer-35-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (please read the precautions on the back first to write this) Page) Binding:

490392 A7 ___B7__ 5. Description of the invention (34) L L D P E thin film, to produce a laminated film. The evaluation results are shown in Table 5. Example 8 Instead of using a 40 Wm sealant CPP (a propylene-ethylene-1-butene ternary random copolymer film with a melting point of 140C, an ethylene content of 3 mole%, and a 1-butene content of 1 mole%) instead of 40 A laminated film was produced in the same manner as in Example 7 except for the non-stretched LLDPE film of / im. The evaluation results are shown in Table 5. Comparative Example 4 A laminated film was produced in the same manner as in Example 7 except that the surface-treated substrate film shown in Table 4 was used. The evaluation results are shown in Table 5. Comparative Example 5 A laminated film was obtained in the same manner as in Example 8 except that the surface-treated substrate film shown in Table 4 was used. The evaluation results are shown in Table 5. (Please read the notes on the back first to write this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 36- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 490392 repair; ㈤iU 补Exemption-"-Ⅴ. Description of the invention (Table 4) Surface treatment Substrate film Resin surface treatment (conditions) Wetting index mN / m Surface thickness (Ra) nm Bonding heat shrinkage rate MD / TD% Haze% d AF processing (6.8) 54 3.0 ◎ 2.5 / 2.2 3 e BN processing (50) 48 F processing (7 · 3) 62 3.0 〇3.3 / 2.3 3 .f AF processing (6 · 2) 41 3.3 ◎ 2 · 8 / 3.0 3 ε AC treatment (10) 40 4.2 〇3.0 / 3.0 3 h BC treatment (25) 47 4.8 X 3 · 4/3 · 3 3 ^ ---- A ------- install ---- ---- Order --------- (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Agricultural C Processing: Corona discharge treatment in air atmosphere ( ), Treatment density ν · ηιίη / ιη2 Ν treatment: Corona discharge treatment () in nitrogen atmosphere, treatment density Wiin / m2 F treatment: flame plasma treatment (), treatment intensity kcal / m2 -37- Paper rule Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 490392 A7 B7 V. Description of invention () 36 Table 5 Printed surface treatment substrate film adhesiveness and oxygen barrier properties of employees ’cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 80% RH cc / m 2 · day · atm heat seal strength kg / 15mm Example 4 d 4 3-Example 5 e 4 3-Example 6 f 3 3-Example 7 d 4 3 3.8 Example 8 d 4 3 2,6 Comparative Example 4 g 1 4 2.0 Comparative Example 5 g 1 4 1.5 Example 9 The resin A shown in Table 1 was extruded using a T-shaped mold, and was used at 2 8 0 1C, standard gauge 4) AS) N (C quasi-standard home country and middle school use a moderate rule of paper on a paper centimeter 29 / X ο 8 Read First-Note on the back S 1

490392 A7 _____B7__ 5. Description of the invention (37) (Please read the precautions on the back before filling out this page) Extruded into a sheet-like shape under heating and melting, and cooled and hardened on a cold hard roll, and then stretched longitudinally by a heated roll stretcher. 4.4 times, and then horizontally extended by 9.5 times with a tenter cross stretcher, heat-hardened for 10 seconds at an ambient temperature of 16.8 ° C, and subjected to 8% relaxation treatment in the TD direction to obtain a biaxial Stretch polypropylene film. Then, flame plasma treatment (treatment intensity: 6.8 kcal / m2) was performed on one surface of the film to obtain a surface-treated substrate film of 20 am. On the surface-treated surface of the obtained surface-treated substrate film, a tackifier (TM 3 2 9 / CAT-8B, manufactured by Toyo Morton Co., Ltd.) 100 parts by weight per 100 weight was applied by a bar coater. Parts, adjusted to a non-volatile content of 10 weight: K) in ethyl acetate solvent, dried at 100¾ for 5 minutes, and left at room temperature for 1 day to prepare a laminated film. The dry weight of the tackified coating was 2 g / m 2. The coating liquid A obtained in Example 1 was applied by a bar coater. After drying, the thickness of the coating layer was 3 // m, and it was dried and hardened at 120¾ for 2 minutes. The evaluation results of the obtained laminated film are shown in Table 6. Examples 10 and 11 and Comparative Examples 6 and 7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A laminated film was produced in the same manner as in Example 9 except that the surface-treated substrate film shown in Table 4 was used. The evaluation results are shown in Table 6. Example 1 2 Except using 100 parts by weight / 6 parts by weight of TAD 3 3 5 A / CAT-10 manufactured by Toyo Morton Co., the nonvolatile component was adjusted to 10 in a mixed solvent of 1 part by weight and 1 part by weight of MEK / methylben. A laminate film was prepared in the same manner as in Example 9 except that the weight% was used as a tackifier. The evaluation results are shown in Table 6. -39- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 490392 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7_ V. Description of the Invention (38) Example 1 3 The surface-treated surface of the surface-treated substrate film prepared in the same manner as in Example 9 was a test coater No. 3 made by Inoue Metal Industries Co., Ltd., a layered tackifier (TM329 / CAT-8B 100 manufactured by Toyo Morton Co., Ltd.) Parts / 100 parts by weight, adjusted to a non-volatile content of 10% by weight in an ethyl acetate solvent, and a dry weight of lg / m2. Then, the coating liquid A obtained in Example 1 was gravure-coated to a dry coating layer thickness of 3 wm. In addition, the above-mentioned tackifier coating agent was laminated to a dry weight of 2 g / m2, and a 40 / im non-stretched LLDPE film was dry-laminated thereon to obtain a laminated film. The evaluation results are shown in Table 6. Example 1 4 Except the use of 20 / im sealant CPP (melting point 140 ° C, ethylene content 3 mol S:, 1-butene content 1 mol% propylene-ethylene-1-butene ternary random copolymerization Material film) instead of a 40 wm unstretched LLDPE film, and a laminated film was prepared in the same manner as in Example 13. The evaluation results are shown in Table 6. Comparative Example 8 A laminated film was produced in the same manner as in Example 13 except that the surface-treated substrate film shown in Table 4 was used. The evaluation results are shown in Table 6. Comparative Example 9 A laminated film was produced in the same manner as in Example 14 except that the surface-treated substrate film shown in Table 4 was used. The evaluation results are shown in Table 6. (Please read the notes on the back first to write this page) rl pack — — — — — — — — —

-40-China National Standard (CNS) A4 Specification (210 X 297 mm) 490392 A7 __B7 V. Description of Invention (39) Table 6 Printed Surface Treatment Substrate Film Adhesive Oxygen Blocking Oxygen Resistance 80S5RH cc / m 2 · day · atm heat seal strength kg / 15mm Example 9 d 4 3 Example 10 e 5 3-Example 11 f 3 3-Example 12 d 4 3 Comparative Example 6 g 2 4- Comparative example 7 h 3 4 Example 13 d 4 2 3.5 Example 14 d 4 3 2 · 5 Comparative example 8 g 2 3 2.8 Comparative example 9 g 1 4 2.0 -41-(Please read the precautions on the back first to write this page ) r 'binding --------- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 490392 A7 B7 V. Description of the invention (M Example 1 5 Make Table 1 show 4 of the resin A using a τ mold extruder, extruded into an M-plate shape under 28 °, heating and melting, and after cooling and hardening on a cold hard roll, it was stretched 4.4 times by a heated roll stretcher to obtain a shaft. Extension sheet. Resin D shown in Table 1 and Yumex 1001 (maleic anhydride modified polypropylene manufactured by Sanyo Chemical Industry Co., Ltd .: not saturated) A mixed resin of 0.5 Wt! U with a monomer unit of organic anhydride (D / Umax 1001 = 80/20 (wU / wU)) is used as the anhydride-modified polypropylene layer through a T-die extruder. It is extruded into a slab shape under heating and melting at 230 ° C. The two-layer slab is made by bonding the above-mentioned one-axis extension sheet on a chill roll, and then stretched to 9.5 times by M with a tenter cross stretcher. Then, it was thermally hardened at an atmosphere temperature of 168 ° C for 10 seconds, and subjected to 8¾ relaxation treatment in the TD direction to obtain a biaxially stretched polypropylene film. Then, a flame plasma treatment was performed on the side surface of the acid-modified polypropylene layer ( Treatment strength; 6.5 kcal / m2) to obtain a surface-treated substrate film i of 20 / im as described in Table 7. On the surface-treated surface of the obtained film, the coating obtained in Example 1 was applied by a M-bar coater. Liquid A, the thickness of the coating layer after drying was 3 / im, and it was dried and hardened at 120¾ for 2 minutes to obtain a laminated film. Various evaluation results are shown in Table 8. Examples 16 and 17 and Comparative Example 10 A laminated film was prepared in the same manner as in Example 15 except that the surface-treated substrate films shown in Tables 1 and 7 were used. The evaluation results are shown in Table 8. Example 18 42- __ a paper sheet suitable for China National Standard Scale (CNS) A4 size (210 X 297 mm)

Please read the notes on the back before (Fill in # Ϊ 装 麦-Page I Order 4 Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed 490392 A7 _B7 __ ^ _ V. Description of the Invention 41) Using a T-die extruder, the resin A shown in Table 1 is extruded into a sheet shape under heating and melting at 28 °, and after being cooled and hardened on a cold hard roll, it is longitudinally stretched by a heating roll stretcher. A four-axis stretch sheet was made. A mixed resin of resin D shown in Table 1 and Tafuma XR110T (propylene-butene-1-copolymer made by Mitsui Chemicals Co., Ltd.) was used (D / XR110T = 8 0/20 (wt! K / wt! N) was extruded into a slab-like shape by heating and melting at 230 ° C with a T-die extruder, and bonded to the above-mentioned one-axis extension slab on a cold hard roll to obtain a slab shape. The two-layer sheet is then stretched by a tenter horizontal stretcher to a ratio of 9.5 times, and then heat-hardened at an atmospheric temperature of 16 8 1C for 10 seconds, and subjected to 8¾ relaxation treatment in the TD direction. A biaxially stretched polypropylene film was prepared. Then, on one side of the film, a corona discharge was applied in a nitrogen atmosphere. Treatment (treatment density; 48W_min / m2), and then flame plasma treatment (treatment strength; 6kcal / m2), to obtain a surface-treated substrate film 1 of 20 / iin as shown in Table 7. On the surface of the obtained film The coating liquid A obtained in Example 1 was coated on the treated surface with a rod coater, and the thickness of the coating layer after drying was 3 to "1, and it was dried at 120¾ for 2 minutes to obtain a laminated film. Various evaluation results are shown in the table. 8. Example 1 9 Resin B shown in Table 1, Resin D shown in Table 1, and Umex 1 0 1 (maleic anhydride-modified polypropylene, unsaturated organic produced by Sanyo Chemical Industry Co., Ltd. An acid anhydride monomer unit of 1.0 weight S!) Mixed resin (D / Umax 1010 = 80/20 (wt! K / wt%)) using a multilayer T mold extruder, heated and melted under 280, Extruded into a slab-like shape, and cooled and hardened on a cold hard roll, stretched 5 times longitudinally with a heated roll stretcher, and then with a tenter-43-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) -------- lip pack ------ (Please read the notes on the back before filling this page) Order ---------- 490392 A7 ___B7__ V. Send Note (42) After the horizontal stretcher was stretched 9.5 times, it was thermally hardened for 10 seconds at an atmosphere temperature of 168 ° C and subjected to TD direction 8 »: relaxation treatment to obtain a biaxially stretched polypropylene film. Then, in One side of the film was subjected to a corona discharge treatment (treatment density; 50 W_min / m2) under a nitrogen atmosphere to obtain a surface-treated substrate film m of 20 / im as shown in Table 7. The coating solution A obtained in Example 1 was applied on the surface-treated surface of the obtained film by a K-bar coater. The thickness of the coating layer after drying was 3 // m, and the coating was dried at 120 ° C for 2 minutes to obtain Laminated film. The results of various evaluations are shown in Table 8. Example 20 On the surface-treated surface of the surface-treated substrate film prepared in the same manner as in Example 19, the coating liquid obtained in Example 1 was coated with a gravure photograph by a test coater No. 3 manufactured by Inoue Metal Industries, Ltd. A. The thickness of the coating after drying is 3 / im. In addition, a layer thickening coating agent (100 parts by weight / 100 parts by weight of TM32 9 / CAT -8B manufactured by Toyo Morton Co., Ltd., adjusted to a non-volatile content of 10% by weight in an ethyl acetate solvent), and a dry weight of 2g / m2, and a 40 Wm unstretched LLDPE film was dry-laminated thereon to prepare a laminated film. The evaluation results are shown in Table 8. Printed in Example 2 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 Sealant CPP (melting point 140¾, ethylene content 3 mole%, 1-butene content 1 mole S; propylene-ethylene-1-butene three Element random copolymer film) instead of 40 // m unstretched LLDPE film, and except that the surface-treated substrate film i obtained by the same method as in Example 15 was used, a laminated film was prepared in the same manner as in Example 20. . The evaluation results are shown in Table 8. -44- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 490392 A7 B7 90.11.-6 Year 5. Description of the invention (“) Yi Yi Ling _ (s, Mmsl / Yue M

Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, C Medical N Silkworm 51 H— ^? * Γ c_. ≫ — * li I 鞔 藏 iffi > SS ^ m 1 m ^ i Γ〇 Θ • m I-1% 11 Xia I ΐ ^ m §: B ^ I 夂 mrr Said tank 1 * 〇 § rm § 2: 1 i— fTTO i © 0 5 S rm JTTO / ^ v 05 矣 S JT «Gi 〇〇Θ Θ * ^ 1 3C is rm rns 8 1 iyrr rm C £ 1 螂 Bi s rnn g 矣 2 m_ I m 〇Ί 〇oo Ca5 ♦ 〇Γ〇 bn JS5 tO oo m All ingenious translation X 〇 ◎ 〇 o ◎ JVVVli Group Μ 4 ^ · A C5 S Lo k 05 CO Ού In 〇ύ CO 4 ^ • o, ll oo a A ^ »(Please read the notes on the back before filling this page) Install ------- -Order ---------. The size of the private paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 490392 A7 B7 V. Description of the invention (44 ) Table 8 Surface treatment substrate film Adhesiveness Oxygen barrier 80% RH cc / m 2 · day · atm Heat seal strength kg / 15rara Example 15 1 5 3-Example 16 j 5 3 Example 17 k 5 3-Example 18 1 5 3-Example 19 m 5 3-Comparison 10 η 3 4 - Example Example 21 i 5 3 3.0 -4 6 20 m 5 3 3.8 Embodiment - This applies China National Standard Paper Scale (CNS) A4 size (210 χ 297 mm)

490392 A7 B7 4 5. V. Description of the invention (22 9) The surface of the biaxially stretched polypropylene film (X layer) shown in Table 10 is applied with a tack coater (manufactured by Toyo Morton Co., Ltd.) TM 329 / CAT-8B 100 parts by weight / 100 parts by weight, adjusted to a non-volatile content of 10% by weight in an ethyl ester solvent), dried at 2g / m2, and dried at 9010 for 5 minutes, on the coating layer The coating obtained in Example 1 was applied with a bar coater to dry and harden for 5 minutes at 120 ¾ (the layer). The tackified coating agent on the hardened surface was the same as described above. Resin film (Z layer) to produce a laminated film. The evaluation results of the obtained film are shown in Table 12 2. 23 The biaxially stretched polypropylene film and thermoplastic film shown in Table 9 to Table 11 were used. 2 1 The same operation, the evaluation results of the laminate are shown in Table 1 2. 11 Except using Soaroluo 20L monomer as the coating agent, the same operation was performed to produce a laminated film. The evaluation results are shown in the table 1 1 shown. 12 Example printed on the surface of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Transliteration) After the acetic acid was dried to thicken the coating solution A, the laminated resin film shown in 11 was used to remove the resin film. Comparative Example Except Example 21 Comparative Example Use Mongolia F) in alcohol (daily exchange water synthesis) Please read the notes on the back first and write this page. Destones (Knipina (transliteration) made by Knipina (Transliteration) Industrial Co., Ltd.) Ultrasonic waves in water exchanged to disperse into lwt% (Liquid B). Make polyethylene Cosserolu (translated by NL05) manufactured by Synthetic Chemical Co., Ltd. is heated to dissolve into 1 wt% (C solution) in ions. The B solution and C solution are mixed into the same amount of liquid -47-The paper size is applicable to Chinese national standards (CNS ) A4 size (210 X 297 mm) 490392 A7B7 free d d. 5. Description of the invention (46) Except using the above coating liquid, perform the same operation as in Example 21 to obtain a laminated film. The evaluation results are as follows Table 11 shows. Table 9 Copolymerization composition of various types of resin Moore% MFR g / 10min DSC peak apex pentad fraction E polypropylene-1 4 165 0.980 F ethylene-propylene random copolymer ethylene; 4 8 140-G low Density polyethylene 1-butene; 7 2 (190 ° C) 120 — ( (Please read the notes on the back before filling this page) ------------- Order --------- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, 1 4 8 A paper size applicable to China National Standard (CNS) A4 Specification (2) 0 χ 297 mm) 490392 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China. 5. Description of the invention (47) Table 10 Surface treatment substrate film resin surface treatment ( Conditions) Wetness index / Surface thickness (Ra) nm Bonding heat shrinkage rate MD / TD% Haze% 0 AN treatment (50) 47 3.0 ◎ 2.8 / 3.5 3 N treatment: Corona discharge treatment under nitrogen atmosphere () Inner processing density W * min / m2 Table 11 Types of Raw Material Resin Film Thickness Haze Surface Treatment Wetness Index mN / m P; Non-stretched Film F 30 3.5 40 q; Non-stretched Film G 50 4 42 One 4 9 One Paper Size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 『丨 '^ · Packing -------- Order --------- (Please read the precautions on the back before filling This page) 490392 A7 B7 V. Description of the invention (48) Table 12 Thickness of resin layer X layer / Z layer Y layer dry um Oxygen resistance 0% RH / 90% RH cc / m 2 · da y · atm water vapor barrier g / πι 2 · day · atm Example 22 〇 / p 2 2.5 / 9 3.0 Example 23 〇 / q 2 2.5 / 8 2.4 Comparative Example 11 〇 / p 2 4/25 3 · 7 Comparative Example 12 0 / p 1 1/20 2.7 As described above, the laminated film of the present invention has excellent oxygen barrier properties and moisture resistance under high humidity. In addition, it is understood from Comparative Example 11 that only water-soluble hydrazone molecules are used, and Comparative Example 12 that uses a layered inorganic compound-containing resin, it is impossible to have both sufficient oxygen barrier properties and moisture resistance under high humidity. Example 2 4 Polypropylene (MFR; 4 g / lOmin, melting point; 1651C, quintile; 0.980) containing 0.5% by weight of myristic acid diethanolamine was used as a charging preventive agent as a raw material, and extruded using a T mold. Machine, heated and melted at 280 t,-50- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

Read first, memorize 1 © S Printing of clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 490392 A7 __B7 _ v 4 9 V. Description of the invention () Extruded into a sheet shape, cooled and hardened on a cold hardened roll, and extended longitudinally by a heating roll stretcher. 4 It was then stretched 9.5 times by a tenter stretcher, and then heat-hardened at an ambient temperature of 16 8 ° C for 10 seconds, and subjected to 8% relaxation treatment in the TD direction to obtain a biaxially stretched polypropylene. film. Then, on one side of the film, an electric discharge treatment (treatment density; 50W * fflin / m2) was performed under a nitrogen atmosphere to obtain a thermal shrinkage ratio MD / TD; 3.2% / 4.2%, a wetting index, · 4 8 m N / m, 2 Q # m surface treated substrate film. A tack coater (manufactured by Toyo Morton Co., Ltd .; main component AD 3 3 5 AE 100 parts by weight) / hardener CAT-1 G 1 QG weight was applied to the treated surface of the surface-treated substrate film by a rod coater. Parts), the dry film thickness is 1 # m, the coating liquid A obtained in Example 1 is applied, and the thickness of the coating layer after drying is 3 // id. After applying the same thickening coating treatment to the coated surface as described above, it is a random polypropylene containing 0.3% by weight of myristic acid diethanolamine (MFR; 7g / 10min, melting point; 140 °) as an antistatic agent. C, ethylene content 2wt%) as raw materials, laminated 50 / iin two-sided electric treatment (wet index; 40 inN / in (strong treatment) and 37mN / m (weak treatment)) non-stretch polypropylene film to produce a laminated film . The evaluation results are shown in Table 13. In addition, the upper laminated film was made with a non-stretched polypropylene film side as an inner side to make a package, and a cut-out part was added, so that it was not attached to the interior surface. -51- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

490392 Α7Β7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (50) Table 13 Total thickness um Oxygen permeability 0UH / 90% RH Surface inherent resistance 1 〇g Ω Example 24 75 1/5 10 · 8 ADVANTAGE OF THE INVENTION The laminated film of this invention is obtained by making M specific biaxially stretched polypropylene film as a base film, and laminating | stacking a specific composition by a sol-gel method on at least one side of this base film The composite polymer layer not only has good oxygen barrier properties or humidity dependence of oxygen barrier properties, but also has an excellent laminated film with regard to the appearance after heat sealing processing after coating processing or adhesive sealing. Therefore, the laminated film of the present invention is extremely useful not only as a gas barrier film but also widely as a film for food packaging. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

Claims (1)

490392 Announcement of Mao mil ·-6 /, i ·, *. Fuyi Chengli, Patent Application No. 88 1 22026 "Gas-barrier Laminated Film" Patent Case (Amended on November 6, 1990) VI. Patent Application Scope: 1. A gas-barrier laminated film, which is characterized by a biaxially stretched polypropylene film with a thermal shrinkage of less than 5% at 150 ° C in the mechanical axis direction of the film and the direction perpendicular to the film, A polymer gas barrier layer laminated on at least one side, wherein the polymer gas barrier layer is a metal alkoxide oxidized by a coating solution made of a composition containing a water-soluble polymer and a metal alkoxide and / or a silane oxide After the polycondensation of a substance and / or silane oxide, it is obtained by drying and curing. The polycondensate is partially hydrolyzed with at least one alkoxide selected from the group of metal alkoxides and silane oxides. A mixture of organic polymers, a reaction product of the partially hydrolyzed polycondensate and a water-soluble polymer, or a mixture of the partially hydrolyzed polycondensate, a water-soluble polymer, and the reaction product, and the composition thereof Biaxial extension Propylene polyacrylate film as measured by 13C-NMR of the fraction of isotactic pentad linked 0.950~0.995. 2. The gas-barrier laminated film according to item 1 of the scope of patent application, wherein the surface of the biaxially-stretched polypropylene film laminated with a polymer gas-barrier layer is applied with electricity under nitrogen and / or carbon dioxide ambient gas. Halo discharge treatment and / or flame plasma treatment. 3 · If the gas-barrier laminated film of item 1 of the scope of patent application, of which the biaxially stretched polypropylene film with polymer gas-barrier layer side is laminated 490392 6. The surface of the scope of patent application is in nitrogen and / or carbon dioxide After applying corona discharge treatment and / or flame plasma treatment under ambient gas, a tackifying coating is formed on the surface. 4. The gas-barrier laminated film according to item 1 of the scope of patent application, wherein the surface of the biaxially stretched polypropylene film laminated with a polymer gas-barrier layer side has at least one selected from acid-modified polyolefins, containing A layer made of ethylene polyolefin and butene-1 polyolefin, and the surface of the layer is subjected to a corona discharge treatment and / or a flame plasma treatment under an ambient gas of nitrogen and / or carbon dioxide. 5. The gas-barrier laminated film according to item 1 of the scope of patent application, which is a thermoplastic resin film having a polymer gas-barrier layer laminated on the surface. 6. The gas barrier laminated film according to item 丨 of the patent application scope, wherein the surface intrinsic resistance 値 log Ω of at least one surface is 11 or less.