JPH0550568A - Laminated film and manufacture thereof - Google Patents

Abstract

PURPOSE:To prevent the delamination of a laminated film bonded by blocking from the cut end part thereof. CONSTITUTION:An inflation film composed of an inner layer 1a is folded double to be formed into a two-layered structure which is, in turn, cut only at one end thereof. A thermally fused bonded part 2 is formed to the overlapped part of the inner layers 19 of the cut end surface to certainly fix the inner layers to form a laminated film 8a of two-layered constitution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film adhered by blocking and a method for producing the same.

[0002]

2. Description of the Related Art As a packaging material used for packaging bags of photographic light-sensitive materials, a laminated film in which a plurality of film layers are laminated is used. To laminate a plurality of film layers, an adhesive layer is used. It was carried out by direct coating or by the extrusion lamination method. However, the laminated film using such an adhesive or the extrusion laminating method not only has many laminating steps and becomes expensive,
The curling was large, the adhesive strength was too high, and the layers were completely integrated and hardened, and the tear strength was low.

Therefore, the present inventor has proposed a laminated film which adheres in a somewhat flexible state by blocking without using an adhesive or the extrusion laminating method (Japanese Patent Laid-Open No. 64-22544).

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The laminated film disclosed in Japanese Patent No. 544 was extremely preferable in that it had high tear strength, gelbotest strength, impact punching strength, and the like, and that curling did not occur. However, the adhesion due to blocking is unstable, and it may peel off from the cut edge at low temperatures, and in the laminating process and bag-making process when stacking other flexible sheets, the pseudo bonding due to blocking may occur. Adhesion may be peeled off, and malfunctions such as wrinkles, streaks, and swelling may occur, and there is a problem particularly in low winter temperatures and when cooling is strong.

In the present invention, the adhesion by blocking means that the inner surfaces of the inflation film are directly adhered to each other without using an adhesive layer.

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and provide a laminated film adhered by blocking having an appropriate strength which does not always peel off when manufactured under normal circumstances.

[0007]

The present invention has been made to achieve the above object, and the laminated film of the present invention according to claim 1 or 2 is a laminated film in which the inner surface of an inflation film is adhered by blocking. It is characterized in that the cut ends are hot melt bonded.

According to a third aspect of the present invention, in the method for producing a laminated film of the present invention, a cylindrical film formed by the inflation film forming method is flatly pressed by a pressure roll to adhere it by blocking, and then melt-cutting method. It is configured by cutting with.

According to a fourth aspect of the present invention, in the method for producing a laminated film according to the present invention, the cylindrical film formed by the inflation film forming method is heated on its surface and then pressed flat by a pressure roll to be bonded by blocking. It is configured to do.

The method of hot-melt bonding the cut ends of the laminated film adhered by blocking is as follows: laser beam cutting method, ultrasonic cutting method, Flame (flame) cutting method, electric discharge cutting method, heating rotary blade cutting method, heating razor. There is a blade cutting method. Among these, the heating razor blade cutting method is preferable because the equipment is inexpensive and the width can be easily changed, and the temperature thereof is preferably the Bigatt softening point (ASTM D-152) of the inner layer.
5) Around the temperature is preferable, 50 ° C or higher and melting point or lower is preferable, 70 to 150 ° C is particularly preferable, and 80 to 120 ° C is most preferable.

A preferred representative example of the blocking adhesion is pressure bonding by a nip roll (pressure roll) (representative examples of the pressure bonding shape are a flat surface pressure, a point pressure and a plurality of vertical streaks). Pressure, lattice pressure, multiple horizontal streaks, and other various embossed pressures), sandwiched between heated metal rolls and elastic rolls such as heat-resistant rubber rolls or cotton rolls, and various types similar to the above pressure bonding It is carried out by passing it under heat and pressure so as to obtain the adhesive shape. However, the present invention is not limited to the above representative example.

As the metal roll, those subjected to various embossed concavo-convex shapes may be used. The embossed shape is, for example, "Bearon Shibo" issued by Tokyo Bearon KK.
More than 210 species are presented. In addition, even if the entire surface is substantially evenly adhered in a planar shape, it may be adhered in a non-planar shape such as a dot shape, a linear shape, a grid shape, a cloth shape, or the like by partially increasing or decreasing the adhesive strength. Good.

It is preferable to heat the cylindrical film before the blocking adhesion by a pressure roll. As the heating method, the inner surface of the inflation film is heated, the mandrel heating method and the outer surface of the inflation film are heated. , Ring-shaped far-infrared heater heating method, hot air heating method, ring-shaped plural nichrome heat heating method, ring-shaped heater bar heating method and the like. A heating method using a ring-shaped heating device is preferable as the outer surface heating method for inflation, but it goes without saying that a plurality of commercially available linear heating devices may be used.

Further, it is preferable that the heating temperature is around the softening temperature of the inner surface of the inflation film, because adhesion by blocking with appropriate strength can be obtained without deteriorating the appearance of the outer surface of the film. Therefore, it is determined by the film forming speed, the film thickness, the resin composition of the film, and the like. For example, in the case of the inner surface made of L-LDPE resin, the inner surface temperature is 40 ℃ or more, preferably 50 ~ 140
C., particularly preferably 60 to 120.degree.

The inflation film may be a single layer or a multi-layer coextrusion film. In the case of a single-layer inflation film, it is necessary to make a difference in temperature between the inner surface and the outer surface of the film. As a method, for example, a ring die is used to make a temperature difference, or only the outer surface of the film is air-cooled to make a temperature difference.

The resin used in the multi-layer coextrusion inflation film having two or more layers is preferably different in the inner layer that is blocked and the outer layer that is not blocked. The resin used for the inner layer has a low softening point and excellent physical strength. Ethylene copolymer resins, propylene copolymer resins, tackifiers and polyolefin modified resins are preferred. Preferred ethylene copolymer resins for the inner layer are shown below.

Typical examples of the ethylene copolymer resin are shown below. (1) ethylene-vinyl acetate copolymer resin (2) ethylene-propylene copolymer resin (3) ethylene-1-butene copolymer resin (4) ethylene-butadiene copolymer resin (5) ethylene-vinyl chloride Copolymer resin (6) ethylene-methyl methacrylate copolymer resin (7) ethylene-methyl acrylate copolymer resin (8) ethylene-ethyl acrylate copolymer resin (hereinafter,
(Displayed as EEA resin) (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (11) Ionomer resin (copolymer of ethylene and unsaturated acid is cross-linked with a metal such as zinc Resin) (12) Ethylene-α-olefin copolymer resin (L-LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin

Among the ethylene copolymer resins, the film moldability and heat sealability are good, and the bag breaking strength, impact punching strength and tear strength are large.
A resin is preferred.

It is also preferable to blend with other thermoplastic resins, various elastomers, various rubbers, various additives and modifiers in order to adapt them to the required characteristics.

Among the ethylene copolymer resins, an ethylene / α-olefin copolymer resin is particularly preferable, and is a resin generally called a linear low-density polyethylene resin (hereinafter abbreviated as L-LDPE resin). Is.

[0021] L-LDPE (L iner L ow D enaity P oly e tyiene)
The resin is called a third polyethylene resin, and is a low-cost, high-strength resin that meets the demands of the times of energy saving and resource saving, which have the advantages of both medium- and low-pressure polyethylene resins. This resin is a low-pressure method or a high-pressure modified method and has ethylene and an α-containing 3 to 13 carbon atoms, preferably 4 to 10 carbon atoms.
It is a copolymer of olefins and is a polyethylene-based resin having a linear straight chain with a short branch. Preferred α-olefins in terms of physical strength and cost are butene-1, octene-1, hexene-1, 4-methylpentene-1,
Hepten-1 etc. are used.

The density is generally considered to be a low-medium density polyethylene resin, but most commercial products have a density within the range of 0.87 to 0.95 g / cm ³ . Melt index is 0.1-50g / 1
Many are in the range of 0 minutes.

As the polymerization process of the L-LDPE resin, there are a gas phase method using a medium / low pressure apparatus, a liquid phase method and an ionic polymerization method using a high pressure improving apparatus.

Among these L-LDPE resins, the melt index (hereinafter referred to as MI) of 0.8 to 1 is particularly preferable in terms of physical strength, heat seal strength and film moldability.
0g / 10min (ASTM D-1238 190 ℃ measurement value), density 0.870〜
0.940 g / cm ³ (measured by ASTM D-1505 at 23 ° C.), and obtained by liquid phase process and gas phase process of α-olefin having 6 to 8 carbon atoms.

Specific examples of the L-LDPE resin are shown below. Ethylene / Butene-1 Copolymer Resin G Resin and NUC-FLX (UCC) Dow Rex (Dow Chemical Co.) Screamer (DuPont Canada) Marrex (Phillips) Stamilex (DSM) Excellen VL (Sumitomo Chemical) NeoZex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Petrochemical) Nisseki Linilex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene / Hexene-1 Copolymer Resin TUFLIN ( UCC) TUFTHENE (Nippon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultzex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical Co.) Screer ( DuPont Canada Inc. ) MORETEC (Idemitsu Petrochemical)

A particularly preferred representative example is the trade name, in which polyethylene has 6 carbon atoms as an α-olefin side chain.
Of 4-methylpentene-1 introduced by Mitsui Petrochemical Co., Ltd. and 8 carbon atoms as α-olefin side chains
MORETEC of Idemitsu Petrochemical Co., Ltd. that introduced 1 octene-1
There are Stamilex of DSM and Dowlex of Dow Chemical (the above are L-LDPE resins obtained by the co-liquid phase process of four products). Preferred typical examples obtained by the low-pressure gas phase process are trade names, which are TUFLIN and UCC of Nippon Unicar Co., Ltd. in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. There are TUF THENE etc.

In addition, recently released ultra low density linear low density polyethylene resin having a density of less than 0.910 g / cm ³ , eg U
NUC-FLX from CC and Excellen V from Sumitomo Chemical Co., Ltd.
L is also preferable (these two products both use butene-1 having an α-olefin of 4 carbon atoms).

The EEA resin is manufactured by Union Carbide (USA), Nippon Unicar Co., Ltd., Mitsubishi Petrochemical Co., Ltd., Sumitomo Chemical Co., Ltd., Mitsui Polychemical Co., Ltd., etc. .. As specific examples, typical brand names of EEA resins currently marketed by Nippon Unicar Co., Ltd., and their comonomer content, melt index, and density are shown (comonomer content of 6% or more by NUC test method).

[0029]

[Table 1]

Further, since it is a low-polymerization degree polyolefin resin, it imparts tackiness to polyolefin resin or rosin resin having an average molecular weight of 300 to 7000, terpene phenol resin, petroleum resin, coumarone indene resin, styrene resin, phenol resin, etc. A thermoplastic resin containing an agent, in particular, various polyolefin resins including a tackifier and a low polymerization degree polyolefin resin are preferable for surely ensuring blocking adhesion. It is preferable that the total amount of one or more of these resins is 50% by weight or more. In particular, a polyolefin resin containing 50% by weight or more of an ethylene / α-olefin copolymer resin and / or an ethylene / vinyl acetate copolymer resin having a Vicat softening point lower than that of the outer layer by 5 ° C or more is excellent in stable blocking adhesion and physical strength. It is preferable because a laminated film having the same structure can be obtained.

The resin used for the outer layer is preferably a resin having a Vicat softening point higher by 5 ° C. or more than that of the inner layer and having excellent inflation film moldability, physical strength and heat seal suitability, for example, a density of 0.920 g / cm 3. ² or more ethylene / α-olefin copolymer resin, density 0.920 g / cm ³
Homopolyethylene resins, homopolypropylene resins, propylene / α-olefin copolymer resins, polyamide resins such as nylon 6, nylon 66, nylon 11, nylon 12 (including copolymer resins with other resins), polyester resins , A homopolymer of an ethylene / vinyl alcohol copolymer resin, or a blended resin containing at least 50% by weight of one or more of the above resins. In particular, a homopolyethylene resin having a density of 0.920 g / cm ³ or more, an ethylene / α-olefin copolymer resin, a polyamide resin and a polyester resin are preferable.

From the viewpoint of suitability for heat-sealing, α-olefin copolymer resin having 2 to 6 carbon atoms is preferable, ethylene / α-olefin copolymer resin is particularly preferable, and ethylene and C 4-10 carbon atoms are most preferable. It is a copolymer resin with α-olefin, and the content of these resins is preferably 3% by weight or more, particularly preferably 10% by weight or more, and most preferably 15% by weight or more from the viewpoint of ensuring the heat seal strength over time. is there. By using the inflation film of the outer layer using the resin composition containing 15% by weight of the ethylene / α-olefin copolymer resin, it is possible to provide a packaging bag having excellent heat seal strength over time, hot tack property, and physical strength. ..

Carbon black, metal powder (including paste), carbon fiber, conductive polymer, metal fiber, antistatic agent, lubricant and the like can be added to the inflation film for the purpose of improving antistatic property, which is preferable.

The most preferable examples of carbon black as a light-shielding substance according to the raw material are carbon black, furnace black, channel black, anthracene black, acetylene black, Ketjen carbon black, thermal black, lamp black, oil smoke, pine smoke, Animal black and vegetable black are available.
In the present invention, furnace carbon black is preferable for the purpose of improving light-shielding properties, costs, and physical properties, and acetylene carbon black and Ketjen carbon black which is a modified by-product carbon black are preferable as the light-shielding substance that is expensive but has an antistatic effect. .. It is also preferable to mix the former and the latter according to the required characteristics, if necessary. There are various forms such as dry color, liquid color, paste color, master batch pellets, compound color pellets, granular color pellets, etc. in which the light-shielding substance is blended with the polyethylene polymer, but the master batch method using master batch pellets Is preferable in terms of cost and prevention of contamination of the workplace. Japanese Patent Publication No. 40-26196
No. 43-10362 describes a method of dispersing carbon black in a solution of a polymer dissolved in an organic solvent to form a polymer-carbon black masterbatch. Describes how to make a batch. The present inventor also proposed a resin composition for colored masterbatch in JP-A-63-186740.

When the laminated film of the present invention is used as a packaging bag for a light-sensitive material, there is no fog, the increase or decrease in the sensitivity of the light-sensitive material is small, the light-shielding ability is large, and L-LDPE is used.
Even when added to the resin film, carbon black has a pH of 6.0 to 9.0 and average particle size is particularly high, because it is difficult to generate carbon black solids (butsu) and foreign substances that cause pinholes in the film such as fish eyes. Diameter is 10 ~
120 mμ, volatile component is 2.0% or less, cyan compound and sulfur component are 1.0% or less, preferably 0.5% or less, particularly preferably
Furnace carbon black having an oil absorption of 0.1% or less and an oil absorption of 50 ml / 100 g or more is preferable. Channel carbon black is not preferable because it is expensive and contains a lot of fog (particularly, sulfur component) in the photographic light-sensitive material. Even if it is absolutely necessary to use it, the effect on photographic properties should be investigated and the type and amount added should be selected.

Further, as actual carbon black products which can be preferably used in packaging materials for photosensitive materials, the quality of which is particularly deteriorated by oxidizing / reducing substances, for example, carbon black # 20 (B), # manufactured by Mitsubishi Kasei Co., Ltd. 30 (B), # 33
(B), # 40 (B), # 44 (B), # 45 (B), # 50, # 55, # 10
0, # 600, # 2200 (B), # 2400 (B), MA8, MA11, M
A100 etc. are mentioned.

As overseas products, for example, Black Pearls 2, 46, 70, 71, 74, 80, 81, 607, etc. of Cabot Co., R
egal 300, 330, 400, 660, 991, SRF-S, Vulcan 3,
6 etc., Sterling 10, SO, V, S, FT-FF, MT-FF and the like.

Furthermore, United of Ashland Chemical Co., Ltd.
R, BB, 15, 102, 3001, 3004, 3006, 3007, 3008, 300
Examples include, but are not limited to, 9, 3011, 3012, XC-3016, XC-3017, and 3020. Typical examples of the light-shielding substance other than carbon black are iron powder, stainless powder, copper powder, lead powder, and aluminum powder as the metal powder.

Examples of carbon fibers include carbon fibers and silicon carbide fibers. Although it has the effect of improving conductivity and physical properties, it is expensive.

The metal fibers include brass fibers and stainless fibers. Improves conductivity but increases specific gravity and is expensive.

In any case, when it is used as a packaging material for a light-sensitive material (particularly when it is used on the light-sensitive material side), the total amount of sulfur and cyan compounds is 1.0% or less, preferably 0.5% or less, particularly preferably 0.1% or less. %, It is preferable to select a light-shielding substance in order not to deteriorate the photographic properties (fog, sensitivity, gradation, color balance, etc.) of the light-sensitive material.

Representative examples of the antistatic agent used in the present invention are described below. I. Nonionic (= nonionic) (1) Alkylamine derivative: T-B103 (Matsumoto Yushi), T-B1
04 (Matsumoto Yushi) Alkylamide type polyoxyethylene alkylamine: Armostat 31
0 (Lion oil) Tertiary amine (lauryl amine): Armostat 400 (Lion oil) N, N-bis (2-hydroxyethyl cocoamine): Armostat
410 (Lion oil) Tertiary amine: ANTISTATIC 273C, 273, 273E (FineOrg. Ch
em) N-hydroxyhexadecyl-di-ethanol-amine: Belg. P. 654,
049 N-hydroxyoctadecyl-di-ethanol-amine: (National Dis
t.) (2) Fatty acid amide derivative: TB-115 (Matsumoto Yushi), Elegan P100 (Nippon Yushi), Eleek SM-2 (Yoshimura Yushi Kagaku) Oxalic acid-N, N'-distearylamide butyl ester: Hoechst poly Oxyethylene alkylamide (3) Ether type polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nH Polyoxyethylene alkylphenyl ether Special nonionic type: Resistant 104, PE100, 116 ~ 118
(Daiichi Kogyo Seiyaku), Register PE132, 139 (Daiichi Kogyo Seiyaku), Elegan E115, Chemistat 1005 (Nippon Yushi), Eleek BM-1 (Yoshimura Yushi Kagaku), Electrostripper TS, TS2, 3, 5, EA, EA2, 3 (Kao Soap) (4) Polyhydric alcohol ester type glycerin fatty acid ester: Monoguri ((Nippon camphor), TB
-123 (Matsumoto Yushi), Resist 113 (Daiichi Kogyo Seiyaku) Sorbitan fatty acid ester Special ester: Eleek BS-1 (Yoshimura Yushi Kagaku) 1-Hydroxyethyl-2-dodecylglyoxazoline: British cellophane

II. Anionic (1) Sulfonic acids Alkyl sulfonate RSO ₃ Na Alkylbenzene sulfonate Alkyl sulphate ROSO ₃ Na (2) Phosphate ester type alkyl phosphate

III. Cation system (1) Amide type cation: Resist PE300, 401, 402,
406, 411 (Daiichi Kogyo Seiyaku Co., Ltd.) (2) Quaternary ammonium salt Quaternary ammonium chloride Quaternary ammonium sulfate Quaternary ammonium nitrate Katimin CSM-9 (Yoshimura Yushi Kagaku), CATANAC 609 (American cyanamide), Denon 314C (Marubishi Yuka), Armostat 300 (Lion oil), 100V (Armor), Electrostripper-ES (Kao soap), Chemistat 20
09A (Nippon Yushi) Stearamido propyl-dimethyl-β-hydroxyethyl ammoniu
m nitrate: CATANAC / SN (American Theanamid)

IV. Zwitterion type (1) Alkyl petaine type: (2) Imidazoline type: Rheostat 53, 532 (Lion oil), AMS 53 (Lion oil), AMS 303, 313 (Lion oil) Alkyl imidazoline type (3) Metal salt: AMS 576 (Lion oil) Rheostat 826, 923 (Lion oil) (RNR'CH ₂ CH ₂ CH ₂ NCH ₂ COO) ₂ Mg R ≧ C, R '= H or (CH
₂₎ MCOO-: by Lion Yushi R = C ₃ ~ ₈ hydrocarbon, A = oxygen or imino group, M = organic amine or metal (4) alkylalanine type:

V. Conductive resin Polyvinylbenzyl type cation Polyacrylic acid type cation

VI. Others: Register 204, 205 (Daiichi Kogyo Seiyaku), Elegan 2E, 100E (NOF), Chemistat 1002, 1003, 2010 (NOF), Eleek 51
(Yoshimura Oil Chemistry), ALROMINE RV-100 (Geigy)

Among the above antistatic agents, nonionic (nonionic) type antistatic agents are particularly preferable because they have little adverse effect on photographic properties and human body.

The antistatic agent will be specifically described. As the internal antistatic agent mixed and used in the thermoplastic resin, any of nonionic type, anionic type and zwitterionic type may be used.

Specific examples of the nonionic type include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, esters (for example, higher fatty acid and polyhydric alcohol esters, higher fatty acid polyethylene-glycol esters, etc.). ), Polyethers and amides (eg higher fatty acid amides, dialkyl amides, ethylene oxide adducts of higher fatty acid amides, etc.) are effective.

Examples of anionic compounds include alkylallylphosphonic acid, adipic acid, glutamic acid, alkylsulfonates, alkyl sulfates, polyoxyethylene alkyl phosphates, fatty acid salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and sodium dialkyl. Sulfosuccinate is effective.

As for the cationic system, amines (eg, alkylamine phosphate, Schiff base, amidoamine, polyethyleneimine, amidoamine-metal salt complex, amino acid alkyl ester, etc.), imidazolines, amine ethylene oxide adducts. , Quaternary ammonium salts and the like are preferable.

As for the zwitterionic system, N-acyl sarcosinate, aminocarboxylic acid derivatives, alanine type metal salt, imidazoline type metal salt, carboxylic acid type metal salt, dicarboxylic acid type metal salt, diamine type metal salt, A metal salt having an ethylene oxide group is preferable.

Inorganic electrolytes, metal powders, metal oxides, kaolins, silicates, carbon powders, and carbon fibers are also effective in the present invention as substances that do not fall into the above categories. Graft polymerization and polymer blending are also effective.

Typical examples of the antistatic agent for external use include polyhydric alcohols (eg, glycerin, sorbit, polyethylene glycol, polyethylene oxide, etc.), polyhydric alcohol esters, and higher alcohol ethylene in the nonionic system. -Oxide adducts, alkylphenol ethylene oxide adducts,
Fatty acid ethylene oxide adducts, amides, amide oxide ethylene adducts, amine oxide ethylene adducts, etc. are available. In zwitterionic systems, carboxylic acids (eg alkylalanine etc.), sulfonic acids, etc. are effective. ..

In the anionic system, carboxylate, sulfuric acid derivative (eg, alkyl sulfonate, etc.) and phosphoric acid derivative (eg, phosphonic acid, phosphoric acid ester, etc.) polyester derivative are preferable.

In the cationic system, amines (eg, alkylamine, amidoamine, esteramine, etc.), vinyl nitrogen derivative, quaternary ammonium salt (eg, amide group-containing ammonium salt, ethylene oxide-containing ammonium salt, etc.), acrylic acid There are ester derivatives, acrylic acid amide derivatives, vinyl ether derivatives and the like.

Listed below are representative names of commercially available lubricants added to the polyolefin resin film layer of the present invention and manufacturer's names.

(1) Silicone oil lubricants; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone) and polymethylphenylsiloxane, olefin-modified silicone, polyether-modified silicone modified with polyethylene glycol or polypropylene glycol A silicone-based oil containing a modified siloxane bond such as olefin / polyether modified silicone, epoxy modified silicone, amino modified silicone, and alcohol modified silicone. In the silicone oil,
In particular, olefin-modified silicone, polyether-modified silicone, olefin / polyether-modified silicone and the like are excellent. The silicone oil improves the coefficient of friction of the film in a heated state, reduces the sliding resistance generated during hot plate sealing by an automatic packaging machine, and prevents wrinkles from occurring, resulting in a beautiful appearance and high sealing performance. It is possible to form a basis for obtaining a film that retains the performance of having a tight adherence to the packaged object and that does not sag. Further, it is possible to obtain a beautiful seal portion by preventing a decrease in gloss due to sliding. In the present invention in which silicone oil is also used, the high temperature friction coefficient can be 1.4 or less when sliding heat sealing is performed.

The viscosity at room temperature is preferably in the range of 50 to 100,000 centistokes, more preferably 5,000 to 30,
High viscosity of 000 centistokes is good. The addition amount varies depending on the type and purpose of use, but is 0.01 to 2.5% by weight. Preferably 0.03 to 1.0% by weight, particularly preferably 0.05
~ 0.5% by weight.

The effects of the addition of silicone oil are many as the following uses of the present invention. By only using the fibrous filler, the non-fibrous light-shielding substance, and the pigment in combination, the surface of these is covered and the dispersibility is improved. It improves the fluidity of the resin, reduces the motor load on the screw, and prevents melt fracture. Sufficient lubricity can be secured without adding a fatty acid amide that bleeds out to form a white powder. It is possible to reduce the friction coefficient of the film in the heated state, improve the suitability for automatic bag making, prevent wrinkles at the time of heat sealing and deterioration of gloss due to sliding, and obtain a beautiful sealed portion. When used together with a light-shielding substance, the light-shielding ability can be improved, and the light-shielding property can be ensured even if the amount of the light-shielding substance that deteriorates the physical properties is reduced to improve the physical properties. (2) Fatty acid amide type lubricant; (2-1) Saturated fatty acid amide type lubricant Behenic acid amide type lubricant; Diamid KN (Nippon Kasei) etc. Stearic acid amide type lubricant; Armide HT (Lion oil), Alflo S-10 ( Nippon Oil & Fats, Fatty Acid Amide S (Kao), Diamid 200 (Nippon Kasei), Diamid AP-1 (Nippon Kasei), Amide S, Amide T
(Nitto Kagaku), Neutron-2 (Nippon Seika), etc. (2-2) Unsaturated fatty acid amide lubricants, erucic acid amide lubricants; Alflo P-10 (Nippon Yushi), Neutron-S (Nippon Seika) , LUBROL (IC
・ I), Diamid L-200 (Nippon Kasei), etc. Oleic acid amide lubricants; Armoslip CP (Lion Akzo), Neutron (Nippon Seika), Neutron E-18 (Nippon Seika), Amide O (Nitto Kagaku), Diamid O-200, Diamid G-200 (Nippon Kasei), Alflo E-10 (Nippon Yushi), Fatty Acid Amide O (Kao), etc. (2-3) Bisfatty Acid Amide Lubricants Methylenebisbe Henic acid amide lubricant; Diamid NK bis (Nippon Kasei), etc. Methylene bis stearic amide lubricant; Diamid 200 bis (Nippon Kasei), Armowax (Lion
Akzo), bisamide (Nitto Kagaku), etc. Methylenebisoleic acid amide lubricant; Lubron O
(Nippon Kasei) etc. Ethylenebisstearic acid amide lubricant; Armoslip EBS (Lion Akzo) etc. Hexamethylenebisstearic acid amide lubricant; Amide 65 (Kawaken Fine Chemicals) etc. Hexamethylenebisoleic acid amide lubricant; Amide 60 (Kawaken Fine Chemicals), etc. (2-4) Monoalkylolamide lubricant N- (2-hydroxyethyl) lauric acid amide lubricant;
Tohoru N130 (Toho Kagaku) etc. N- (2-hydroxyethyl) stearic amide lubricant; Amizole (Kawaken Fine Chemicals) etc. N- (2-hydroxymethyl) stearic amide lubricant; Methylol amide (Nitto Kagaku) etc. ( 3) Nonionic surfactant lubricant; electrostripper
-TS-2, Electrostriper-TS-3 (Kao soap), etc. (4) Hydrocarbon lubricants; liquid paraffin, natural paraffin, micro wax, synthetic paraffin, polyethylene wax, polypropylene wax, chlorinated hydrocarbon,
Fluorocarboxylic (5) fatty acid-based lubricant; higher fatty acid (C ₁₂ or more is preferable), oxyfatty acid (6) ester-based lubricant; lower alcohol ester of fatty acid, polyhydric alcohol ester of fatty acid, polyglycol ester of fatty acid, fat of fatty acid Alcohol ester (7) Alcohol-based lubricant; polyhydric alcohol, polyglycol, polyglycerol (8) Metal soap; higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid and oleic acid, and Li,
Compounds with metals such as Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn and Pb. For example, calcium stearate, zinc stearate, cadmium stearate, calcium oleate, magnesium oleate, etc.

The above-mentioned lubricant is preferably added in an amount of 0.01 to 5.0% by weight. In the case of a fatty acid amide type lubricant which has a large lubricating effect and is easy to bleed out, the amount is reduced to 0.01 to 1.0% by weight, and the necessary minimum amount is added. Is preferred.

The laminated film of the present invention comprises various light-sensitive materials,
Various packaging bags for foods, pharmaceuticals, dyes, resins, concentrated products, fish meal, fertilizers, cement, explosives, product cover films, pesticide multi-films, waterproof films, moisture-proof films, light-proof films, cold-proof films, heat-proof films, etc. It can be used as a packaging material.

On the other hand, considering the case of landfilling as waste, degradable plastics that are currently being researched or are introduced into some markets may be used. For example, as a biodegradable polymer, IC
Polymer "BIOPOL" manufactured by Company I, "Polycaprolactone manufactured by UCC", or a polymer or starch-containing heat that is indirectly disintegrated by adding natural or synthetic polymer that is susceptible to biodegradation as an additive. Plastic resins such as various ethylene copolymer resins and various polyethylene resins can also be used.

It is also possible to use a photodegradable polymer. For example, an ECO copolymer obtained by copolymerizing ethylene and carbon monoxide into which a carbonyl group is introduced as a photosensitizing group in the main chain during polyethylene polymerization is used, or a transition metal salt, an oxidation accelerator, and a photosensitizer are used as additives. It is possible to use a material obtained by adding a material or the like to the base polymer and imparting photodegradability thereto.

Typical examples of the light-sensitive material are shown below. (a) Silver halide photographic light-sensitive material (X-ray photographic film, printing film (lith film), black and white and color photographic paper, color film, master paper for printing, DTR photographic material, computer typesetting film and paper, microfilm, movie) Film, self-developing photographic light-sensitive material, direct positive film and paper, etc.) (b) Diazonium photographic light-sensitive material (4-morpholinobenzenediazonium microfilm, microfilm,
Copying film, printing plate material, etc. (c) Azide-, diazide-based photographic light-sensitive material (para-azidobenzoede, light-sensitive material containing 4,4'diazidostilbene, etc.,
(For example, copying films, printing plate materials, etc.) (d) Quinonediazide photographic light-sensitive materials (orthoquinonediazide, orthonaphthoquinonediazide compounds, such as benzoquinone (1,2) -diazide- (2) -4-sulfonic acid phenyl ether) A photosensitive material containing, for example, a printing plate material,
(Copying film, adhesion film, etc.) (e) Photopolymer (photosensitive material containing vinyl monomer, printing plate material, adhesion film, etc.) (f) Polyvinyl cinnamate (for printing film, IC, etc.) Resist etc.) Photosensitive substances that are altered or deteriorated by various light, oxygen, sulfurous acid gas, etc., such as food (butter, peanut, margarine, snack products, knobs, confectionery, tea, paste, etc.), medical products (gastrointestinal drug, The present invention can also be applied to packaging of powdered or granular bag-like chemicals such as a cold medicine, ABS resin, dyes, pigments, photographic developing chemicals, photographic fixing chemicals, toners and the like.

The packaging form applied to the packaging material for photographic light-sensitive materials using the laminated film of the present invention is a single flat bag,
Double flat bag, freestanding bag, single gusset bag, double gusset bag,
In addition to packaging bags such as standing pouches and handbags, there are laminated films, moisture-proof boxes inside, light-room loading light-shielding magazine inside, magazineless light-room loading light-shielding members, leader paper, etc. The method for making the bag is a conventionally known method for adhering a plastic film such as a hot plate adhering method, an impulse adhering method, a fusing adhering method, an ultrasonic adhering method, a high frequency adhering method. In addition,
It is also possible to make a bag by an adhesive method using an adhesive, a pressure-sensitive adhesive, or an adhesive method using a pressure-sensitive / heat-sensitive adhesive.

Further, the laminated film of the present invention according to claim 5 is a laminated film in which the inner surface of an inner layer of an inflation film consisting of an inner layer and an outer layer is adhered by blocking, the shore hardness of the inner layer being higher than that of the thermoplastic resin of the outer layer. It is characterized by containing a low thermoplastic resin of ASTM D-2240).

Further, the laminated film of the present invention according to claim 6 is an inflation film comprising an inner layer and an outer layer, wherein the inner surface of the inner layer is adhered by blocking, and the inner layer contains an acid-modified polyolefin resin. It is configured with.

The shore hardness of the thermoplastic resin having a low shore hardness contained in the inner layer is preferably 60 D or less, and particularly preferably in the range of 10 to 50 D, from the viewpoints of securing adhesion by blocking, flexibility and securing gelbotest strength. And it is preferable that the Shore hardness of the thermoplastic resin contained in the outer layer is lower than the Shore hardness by 2D or more, especially 5D or more.

Examples of the thermoplastic resin as described above include acid-modified polyolefin resin, L-LDPE resin, EEA resin, EV
Polyolefin copolymer resins such as A resin are preferred.

The acid-modified polyolefin resin is a modified resin obtained by graft-modifying a polyolefin resin and unsaturated carboxylic acids, and examples thereof include graft-modified polyethylene resin, graft-modified, ethylene / ethyl acrylate copolymer resin, graft-modified ethylene / acetic acid. Vinyl copolymer resin,
Graft-modified polypropylene resin and polybutene-1,
Examples include resins obtained by graft-modifying an α-olefin such as poly-4-methylpentene-1 or an ethylene / α-olefin copolymer resin with an unsaturated carboxylic acid or the like. A graft-modified polyolefin resin obtained by grafting an unsaturated carboxylic acid such as acrylic acid, maleic acid or maleic anhydride onto a polyolefin resin is preferable.

The graft ratio of unsaturated carboxylic acids is 0.01
It is preferably -10%. The unsaturated carboxylic acids are
It is a generic name including its derivatives. Typical examples are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, mesaconic acid,
Angelic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, itaconic anhydride , Methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester,
Fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid diethyl ester, acrylic acid amide,
Methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid Monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-diethylamide, fumaric acid-
N-monobutyramide, fumaric acid-N, N-dibutyramide,
Maleimide, monomethyl maleate, dimethyl maleate, potassium matacrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, N-butyl maleimide, N-phenyl Maleimide, maleenyl chloride, glycidyl maleate, dipropyl maleate, aconitic acid anhydride, sorbic acid, etc. can be mentioned, and they can be mixed and used. Of these, acrylic acid, maleic acid, maleic anhydride, and nadic acid are preferable, and maleic anhydride is particularly preferable.

The method for graft-modifying unsaturated carboxylic acids in the acid-modified polyolefin resin is not particularly limited. For example, Japanese Examined Patent Publication No. 43-2742 which reacts in a molten state
No. 1 or the like, the method disclosed in JP-B-44-15422 or the like to react in a solution state, or the method disclosed in JP-B-43-18144 or the like to react in a slurry state,
There is a method disclosed in Japanese Patent Publication No. 50-77493, which reacts in a gas phase. Among these methods, the melt-kneading method using an extruder is preferable because the operation is simple and inexpensive.

The amount of unsaturated carboxylic acids used is a polyolefin resin base polymer (various polyethylene resins, polypropylene resins, polyolefin copolymer resins, polybutene-1 resin, poly-4-methylpentene-1) for securing adhesive strength. (Alpha resin such as resin) 0.01 to 20 parts by weight is preferable with respect to 100 parts by weight, especially 0.2 to 5
Parts by weight are preferred.

A peroxide or the like can be used to accelerate the reaction between the polyolefin resin and the unsaturated carboxylic acid.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, α, α '.
Bis (t-butylperoxydipropyl) benzene, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane,
2,5-Dimethyl-2,5-di (t-butylperoxy) hexine, di-t-butylperoxide, cumene hydroperoxide, t-butyl-hydroperoxide, dicumyl peroxide, t-butylperoxide Oxylaurate, t-
Butyl peroxy benzoate, 1,3 bis (t-butyl peroxy isopropyl) benzene, cumene hydroperoxide, di-t-butyl-diperoxy phthalate,
Examples include t-butyl peroxymaleic acid and isopropyl percarbonate. Examples of the inorganic peroxide include azo compounds such as azobisisobutyronitrile and ammonium persulfate.

These may be used alone or in combination of two or more. Particularly preferred is a decomposition temperature of 170 ° C to 2
Di-t-butylperoxide, di-cumylperoxide, 2,5-dimethyl-2,5di (t-butylperoxy) hexane, 2,5-dimethyl-2,5di ( t-butylperoxy) hexyne and 1,3-bis (t-butylperoxyisopropyl) benzene.

The addition amount of these peroxides is not particularly limited, but 0.005 to 100 parts by weight of the polyolefin resin is added.
It is preferably 5 parts by weight, particularly preferably 0.01 to 1 part by weight.

Representative examples of commercially available acid-modified polyolefin resins are shown below. Nippon Petrochemical KK “N Polymer” Mitsui Petrochemical KK “ADMER” Showa Denko KK “ER RESIN” Mitsubishi Kasei KK “Novatech-AP” Mitsubishi Yuka KK “MODIC” Nippon Unicar KK “NUC-ACE”

Examples of the polyolefin resin include polyethylene resin, ethylene copolymer resin, polypropylene resin, propylene copolymer resin and vinyl chloride resin. In particular, ethylene copolymer resin is preferable because it improves heat sealability, bag breaking strength, and impact punching strength.

The acid-modified polyolefin resin as described above is contained in the inner layer, but the content is preferably 5 to 80% by weight, particularly preferably 10 to 60% by weight. When the content is less than 5% by weight, it is difficult to always cause the adhesion by blocking on the entire inner surface of the inner layer, and it is difficult to exert the effect of improving the dispersibility of the light-shielding substance. Furthermore, when a polyester resin, a polyamide resin, or an ethylene / vinyl alcohol copolymer resin is used for the outer layer, delamination occurs at the boundary between the outer layer and the inner layer, which makes practical application difficult. If the content exceeds 80% by weight, adhesion due to blocking can be generated on the entire surface, and the effect of improving the dispersibility of the light-shielding substance can be increased, but it not only adversely affects the photographic light-sensitive material but also the mold. The detergency deteriorates, the cost becomes high, and it is difficult to put into practical use.

As resins other than the acid-modified polyolefin resin contained in the inner layer, there are various resins that can be blended with the acid-modified polyolefin resin, such as various thermoplastic resins, various elastomers, tackifying resins, etc. Polyolefin resins such as excellent various ethylene copolymer resins, various propylene copolymer resins, homopolyethylene resins, and homopolypropylene resins are preferable. Especially L-LDPE
Resin, EEA resin, EVA resin and LDPE resin are preferred.
Among these resins, those having a low Shore hardness and a low Vicat softening point are particularly preferable.

The laminated film of the present invention according to claim 7 is
The outer layer has a higher Vicat softening point (ASTM D-1525) than the inner layer,
And it has heat sealability.

As the resin used for the outer layer, there are various thermoplastic resins, various elastomers, etc., but it is necessary to select a resin having higher antiblocking property, abrasion resistance, shore hardness and Vicat softening point than the inner layer. In addition, the heat-sealed application, for example, a laminated film used for a bag needs to have a heat-sealing property, and when used for a photographic light-sensitive material, a resin that does not adversely affect photographic performance is selected. There is a need. When heat sealability is required, various polyolefin resins having higher Shore hardness and Vicat softening point than the resin used for the inner layer, polyester resins having heat sealability are preferable, and when heat sealability is not required, various polyamide resins are used. , Various polyester resins, high molecular weight polyethylene resins, and high molecular weight polypropylene resins are preferable.

The Shore hardness of the resin used for the outer layer is 2D as compared with the Shore hardness of the resin used for the inner layer.
As described above, it is preferably 5D or more. The Shore hardness is 50 D or more, preferably 60 D or more, and particularly preferably 70 D or more. In any case, the resin is 2D or more higher than the Shore hardness of the inner layer.

Further, the laminated film of the present invention according to claim 7 is characterized in that the outer layer has a higher Vicat softening point than the inner layer and has heat sealability.

The Vicat softening point of the outer layer is equal to or higher than the Vicat softening point of the inner layer. Suitability for heat sealing during bag making (appearance, prevention of pinholes and breakage due to melting of the outer layer, strength reduction, etc.). From the viewpoint of, especially 5 ℃
It is preferably higher than the Vicat softening point of the inner layer. Prevents deterioration of physical strength of the heat-sealed part with excellent appearance,
In order to improve the bag-making speed, it is preferably higher than the Vicat softening point of the inner layer by 10 ° C. or more.

The laminated film of the present invention according to claim 8 is
Young's modulus (ASTM D-882) on the surface is 50 kg / mm ² or more, and heat resistance (a melting point of 100 ° C. or more or a flexible sheet such as paper, cellophane, cloth, etc. is said to be heat resistant in the present invention) Of the flexible sheet, the cut end portion of which is adhered by blocking is laminated by heat fusion and the laminated film with or without an adhesive layer.

The flexible sheet to be laminated on the surface is a thermoplastic resin film such as various polyethylene resins, ethylene copolymer resins, polypropylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyamide resins, polycarbonate resins, polyester resins. And the like, known modified films thereof, modified resin films thereof and uniaxially or biaxially stretched films thereof. Further, cellulose acetate film, cellophane, regenerated cellulose film, ethylene / vinyl alcohol copolymer resin film (Eval resin film), paper, synthetic paper, non-woven fabric and the like may be used.

Particularly preferred flexible sheets are various types of paper (unbleached kraft paper, semi-bleached kraft paper, unbleached kraft paper, which is heat resistant and does not melt (has no melting point) and does not affect the photosensitive material and has a basis weight of 20 to 400 g / m ² . Bleached kraft paper, high-yield pulp paper, neutral paper,
(Hinelli base paper, Kurupak paper, Duo stress paper, white paperboard, photographic base paper, pure white roll paper, coated paper, waste paper, recycled paper, imitation paper, glassine paper).

These papers may be subjected to various printings, various surface treatments (coating of pigment layer, coating of resin layer, vapor deposition of metal, etc.) and various colors. In order to have a light-shielding property, various types of light-shielding substances may be added, or the surface of the paper may be coated, and various types of patterning may be applied as necessary.

Other preferable heat-resistant flexible sheets include biaxially stretched thermoplastic resin film and cellophane. Depending on the application, a uniaxially stretched thermoplastic resin film is also preferable.

The biaxially stretched thermoplastic resin film is formed by a well-known biaxial stretching method such as simultaneous biaxial stretching or sequential biaxial stretching, in the vertical direction (MD direction) and the horizontal direction (CD direction).
The film is stretched 1.5 to 20 times, preferably 3 to 15 times. The thermoplastic resin used for this film includes various polyester resins, various polyamide (nylon) resins, various polyethylene resins, various polystyrene resins, various polypropylene resins, various polyolefin copolymer resins, polyvinyl chloride resins, polyvinylidene chloride resins. , Ethylene / vinyl alcohol copolymer resin, ethylene / vinyl acetate copolymer saponified resin, polyacrylonitrile resin, vinylon resin, etc. and copolymer resins of these resins and other resins (only binary copolymer resin However, it contains a ternary or higher copolymer resin (the copolymer may be either random copolymer or block copolymer),
It is a mixed resin of the above resin and another resin. The resin used for the uniaxially stretched thermoplastic resin film is also the above resin.

The above-mentioned various polyester resins include resins synthesized from dimethyl terephthalate and ethylene glycol, dimethyl terephthalate and 1,4-cyclohexanedimethanol, dimethyl terephthalate and dimethyl isophthalate. Nylon 6, nylon 66, nylon 12, nylon 11, nylon 6 for various polyamide resins
-66 copolymer resin, etc.

Then, these resins are biaxially stretched by a T-die film molding machine or an inflation film molding machine to form a film.

The surface of the uniaxially or biaxially stretched thermoplastic resin film and cellophane may be subjected to metal vapor deposition, coating with a vinylidene chloride resin layer, or the like, and may be subjected to various kinds of printing or coloring in various colors. Good. For the purpose of improving lubricity and printability, various types of patterns may be applied to the surface.

The thickness of the biaxially stretched thermoplastic resin film is preferably 5 to 70 μm, particularly preferably 7 to 50 μm, and 10 to 10 μm in order to make the packaging material thin, reduce costs, and ensure flexibility and physical strength. 35 μm is most preferable. Thickness is 5μ
If it is less than m, wrinkles and cuts are likely to occur in the laminating step, and if it exceeds 70 μm, the rigidity is too high, the suitability for bag making is deteriorated, and the gel botest strength and handleability are deteriorated and the cost becomes high.

The flexible sheet has a Young's modulus (ASTM
D-882) is preferably high, 50 kg / mm ² or more, preferably 80 kg / mm ² or more, and particularly preferably 100 kg / mm ² .

The flexible sheet preferably has heat resistance, and this heat resistance is 50 ° C. or more, especially 10 ° C. or more than that of the outer layer to be heat-sealed from the viewpoints of suitability for bag making and appearance improvement. It is preferable to have

The Young's modulus (AS
TM D-882) is 50 kg / mm ² or more, preferably 80 kg / mm ² or more,
Particularly preferably, typical examples of heat-resistant flexible sheets having a resistance of 100 kg / mm ² or more are shown below.

Flexible sheet name Young's modulus (kg / mm ² ) Melting point (° C) Biaxially stretched high density polyethylene film 80 to 90 137 Unstretched polypropylene film 60 to 90 140 Biaxially stretched polypropylene film 150 to 350 175 Vinylidene chloride coat 2 Axial oriented polypropylene film 170-260 175 Biaxially oriented polyamide film 130-280 225 Biaxially oriented polyester film 190-400 260 Cellophane 140-210 150 (carbonized) Vinylidene chloride cellophane 160-320 150 (carbonized) Ethylene / vinyl alcohol 190 ~ 350 180 Copolymer film Biaxially oriented polystyrene film 280 ~ 390 160 Polycarbonate film 230 ~ 240 220 Cellulose acetate film 50 ~ 280 260 or more Kraft paper 350 or more 260 or more

The flexible sheet is laminated on the outer layer with or without an adhesive layer. The adhesive layer for laminating the flexible sheet is usually an adhesive layer formed by a generally used wet laminating method, dry laminating method, hot melt laminating method, extrusion laminating method, co-extrusion extrusion laminating method or the like. Various thermoplastic resins that can be used but have few volatile substances that are likely to adversely affect photographic light-sensitive materials, especially polyolefin-based thermoplastic resins (for example, low-density homopolyethylene resin, L-LDPE resin, EEA resin, EAA resin, EVA) An extrusion laminate adhesive layer using a resin, an acid-modified polyolefin resin, or a resin containing 50% or more of one or more of a propylene copolymer resin is preferable.

The adhesive layer has a thickness of 1 to 50 μm, preferably 2 to 30 μm, particularly preferably 3 to 10 μm. When the thickness is less than 1 μm, film breakage occurs and the adhesive force to the heat resistant support cannot be secured. If the thickness exceeds 50 μm, not only becomes expensive but also the neck-in becomes large.

A heat seal layer can be laminated on the surface of the laminated film of the present invention according to claim 9. This heat seal layer has a Vicat softening point (ASTM D-15
25) is preferably low, particularly preferably 5 ° C. or higher, and most preferably 10 ° C. or higher.

As the resin used for the heat seal layer, there are various thermoplastic resins having heat sealability, but various polyolefin resins are preferable, and low density homopolyethylene resin and various ethylene copolymer resins are particularly preferable. Representative examples of particularly preferable ethylene copolymer resins are shown below. (1) Ethylene-vinyl acetate copolymer resin (2) Ethylene-propylene copolymer resin (3) Ethylene-1-butene copolymer resin (4) Ethylene-butadiene copolymer resin (5) Ethylene-vinyl chloride Copolymer resin (6) ethylene-methyl methacrylate copolymer resin (7) ethylene-methyl acrylate copolymer resin (8) ethylene-ethyl acrylate copolymer resin (hereinafter
(Displayed as EEA resin) (9) Ethylene-acrylonitrile copolymer resin (10) Ethylene-acrylic acid copolymer resin (11) Ionomer resin (copolymer of ethylene and unsaturated acid is cross-linked with a metal such as zinc Resin) (12) Ethylene-α-olefin copolymer resin (L-LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin In ethylene copolymer resin, film moldability and heat seal suitability The L-LDPE resin and the EEA resin are preferable because they have good bag breaking strength, impact punching strength and tear strength.

Further, in order to adapt to the required characteristics, it is also preferable to use it by blending it with other thermoplastic resins, various elastomers, various rubbers, various additives and modifiers.

Among the ethylene copolymer resins, an ethylene / α-olefin copolymer resin is particularly preferable, and a resin generally called a linear low-density polyethylene resin (hereinafter, abbreviated as L-LDPE resin). Is.

[0109] L-LDPE (L iner L ow D enaity P oly e tyiene)
The resin is called the third polyethylene resin, and is a low-cost, high-strength resin that meets the demands of the times of energy saving and resource saving, which have the advantages of both medium- and low-pressure method polyethylene resins. This resin is a low-pressure method or a high-pressure modified method and has ethylene and an α-containing 3 to 13 carbon atoms, preferably 4 to 10 carbon atoms.
It is a copolymer of olefins and is a polyethylene-based resin having a linear straight chain with a short branch. Preferred α-olefins in terms of physical strength and cost are butene-1, octene-1, hexene-1, 4-methylpentene-1,
Hepten-1 etc. are used.

The density is generally considered to be a low-medium density polyethylene resin, but many commercial products have a density in the range of 0.87 to 0.95 g / cm ³ . Melt index is 0.1-50g / 1
Many are in the range of 0 minutes.

As the polymerization process of L-LDPE resin, there are a gas phase method using a medium / low pressure apparatus, a liquid phase method and an ionic polymerization method using a high pressure improving apparatus.

Among these L-LDPE resins, those having a melt index (hereinafter referred to as MI) of 0.8 to 1 are particularly preferable in terms of physical strength, heat seal strength and film moldability.
0g / 10min (ASTM D-1238 190 ℃ measurement value), density 0.870〜
0.940 g / cm ³ (measured by ASTM D-1505 at 23 ° C.), and obtained by liquid phase process and gas phase process of α-olefin having 6 to 8 carbon atoms.

Specific examples of the L-LDPE resin are shown below. Ethylene / Butene-1 Copolymer Resin G Resin and NUC-FLX (UCC) Dow Rex (Dow Chemical Co.) Screamer (DuPont Canada) Marrex (Phillips) Stamilex (DSM) Excellen VL (Sumitomo Chemical) NeoZex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Petrochemical) Nisseki Linilex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene / Hexene-1 Copolymer Resin TUFLIN ( UCC) TUFTHENE (Nippon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultzex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical Co.) Screer ( DuPont Canada Inc. ) MORETEC (Idemitsu Petrochemical)

A particularly preferred representative example is a trade name, in which polyethylene has 6 carbon atoms as an α-olefin side chain.
Of 4-methylpentene-1 introduced by Mitsui Petrochemical Co., Ltd. and 8 carbon atoms as α-olefin side chains
MORETEC of Idemitsu Petrochemical Co., Ltd. that introduced 1 octene-1
There are Stamilex of DSM and Dowlex of Dow Chemical (the above are L-LDPE resins obtained by the co-liquid phase process of four companies). Preferred typical examples obtained by the low-pressure gas phase process are trade names, which are TUFLIN and UCC of Nippon Unicar Co., Ltd. in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. There are TUF THENE etc.

In addition, recently released ultra low density linear low density polyethylene resin having a density of less than 0.910 g / cm ³ , such as U
NUC-FLX from CC and Excellen V from Sumitomo Chemical Co., Ltd.
L is also preferable (these two products both use butene-1 having an α-olefin of 4 carbon atoms).

Representative manufacturers of the EEA resin are Union Carbide (USA), Nippon Unicar Co., Ltd., Mitsubishi Petrochemical Co., Ltd., Sumitomo Chemical Co., Ltd., Mitsui Polychemical Co., Ltd., etc. .. As specific examples, typical brand names of EEA resins currently marketed by Nippon Unicar Co., Ltd., and their comonomer content, melt index, and density are shown (comonomer content of 6% or more by NUC test method).

[0117]

[Table 2]

By containing the ethylene copolymer resin in an amount of 5% by weight or more, preferably 10% by weight or more, it is possible to prevent the heat seal strength from being deteriorated with time.

The method for producing a laminated film of the present invention according to claim 10 is a blocking roll in which a cylindrical film formed by an inflation film forming method is molded with a pressure roll in a non-planar manner so that the adhesive strength is weakened. The cut end of the laminated film adhered by means of the above is melt-bonded by heat.

[0120] As a mold, a dot shape, a plurality of vertical streaks, a lattice shape, a plurality of horizontal streaks, a cloth shape, and various other shapes (for example, a typical embossed shape is "Bearon Shibo" issued by Tokyo Bearon KK 210 (More than one kind has been presented) embossed metal roll (may be heated or at room temperature, but heating is preferable because blocking adhesion is stable, heating temperature is below the melting point, before and after the softening point (Preferably) and an elastic roll such as a heat-resistant rubber roll or a cotton roll, and passed under pressure (heating if necessary).

In the laminated film as described above, the blocking adhesion, the heating method, the heating temperature, the additives such as carbon black, the usage, etc. are the same as those of the laminated film described first.

[0122]

The laminated film of the present invention according to claims 1 and 2 is a laminated film in which the inner surface of an inflation film is adhered by blocking, and in the laminated film in which the cut end is thermally melted, the heat-melted adhesive portion is the inner layer. They firmly adhere to each other and prevent the inner layers from coming off.

In the method for producing a laminated film of the present invention according to claim 3, the cylindrical film formed by the inflation film forming method is pressed flatly by a pressure roll to be bonded by blocking, and then the film is formed by the melt cutting method. By cutting, the hot-melt adhesive portion is firmly fixed and the inner layers are prevented from being separated from each other.

Further, in the method for producing a laminated film of the present invention according to claim 4, the cylindrical film formed by the inflation film forming method is adhered by blocking after heating the surface and pressing it flatly with a pressure roll. In the method for producing a laminated film, the blocking adhesion is improved by heating before pressing with a pressure roll.

Further, the laminated film of the present invention according to claim 5 is a laminated film in which the inner surface of an inflation film composed of an inner layer and an outer layer is adhered by blocking, and the inner layer is made of a thermoplastic resin having a Shore hardness lower than that of the thermoplastic resin of the outer layer. Since the plastic resin is included, the inner layers are firmly bonded to each other.

The laminated film of the present invention according to claim 6 is a laminated film in which the inner surface of an inflation film composed of an inner layer and an outer layer is adhered by blocking, and the inner layer contains an acid-modified polyolefin resin. The two are firmly attached to each other.

Further, in the laminated film of the present invention according to claim 7, the outer layer has a higher Vicat softening point than the inner layer and has heat sealability, so that the inner layers are heated and firmly bonded to each other. Even if pressure is applied, pinholes do not occur, and appearance is not impaired, improving bag making suitability.

The laminated film of the present invention according to claim 8 has a Young's modulus of 50 kg / mm ² or more and a heat-resistant flexible sheet laminated on the surface thereof. Prevents the occurrence of pinholes, improves wear resistance and impact strength, and keeps the appearance beautiful. Further, the inner layers are firmly adhered to each other so as not to be peeled off. Further, the laminated film of the present invention according to claim 9 has a Vicat softening point lower than the outer layer and a heat-sealable heat-sealing layer is laminated on the surface to be heat-sealed, so that heat-sealing can be performed at a low temperature. Therefore, the occurrence of pinholes and the deterioration of appearance are prevented.

Further, in the method for producing a laminated film of the present invention according to claim 10, a cylindrical film formed by an inflation film forming method is pressed in a non-planar manner by a pressure roll having a mold to make the adhesive strength strong and weak. By adhering by blocking, the blocking adhesion between the inner surfaces is improved.

[0130]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the laminated film of the present invention will be described with reference to the drawings. FIG. 1 to FIG. 8 are partial cross-sectional views showing the layer structure of the laminated film of the present invention, in which the cut ends are hot melt bonded.

The laminated film 8a shown in FIG. 1 is formed by folding a single-layer inflation film composed of the inner layer 1a and blocking and adhering it, and cutting only one side to form two layers, and the cut end faces of the inner layer 1a overlap each other. A hot-melt adhesive portion 2 is formed at the portion so that the inner layers 1a are firmly fixed to each other.

The laminated film 8a shown in FIG. 2 is a two-layer coextrusion inflation film composed of an inner layer 1a and an outer layer 3a.
9a is folded back and blocking-adhered, and only one side is cut to form four layers, and the hot-melt adhesive portion 2 is similarly formed at the overlapping portion of the inner layer 1a.

In the laminated film 8a shown in FIG. 3, a three-layer coextrusion inflation film 10a consisting of an inner layer 1a, an intermediate layer 4 and an outer layer 3a is folded back and blocking-adhered, and only one of them is cut into six layers. The inner layer
The hot-melt adhesive portion 2 is similarly formed at the overlapping portion of 1a.

The laminated film 8a shown in FIG. 4 is formed by folding a single layer inflation film composed of the inner layer 1a and blocking and adhering it, and cutting both ends to form two layers. The hot-melt adhesive portion 2 is formed at the overlapping portion so that the inner layers 1a are securely fixed to each other.

The laminated film 8a shown in FIG. 5 is a two-layer coextrusion inflation film composed of an inner layer 1a and an outer layer 3a.
9a is folded back and subjected to blocking adhesion, and both ends are cut to form four layers, and the hot-melt adhesive section 2 is similarly formed in the overlapping portion of the inner layer 1a.

In the laminated film 8a shown in FIG. 6, a three-layer coextrusion inflation film 10a composed of an inner layer 1a, an intermediate layer 4 and an outer layer 3a is folded back and bonded by blocking, and both ends are cut to form six layers. The inner layer 1a
Similarly, the hot-melt adhesive portion 2 is formed at the overlapping portion.

In the laminated film shown in FIG. 7, the flexible sheet 6 is laminated on the laminated film 8a shown in FIG. 2 via the adhesive layer 5.

In the laminated film shown in FIG. 8, the heat seal layer 7 is directly laminated on the laminated film 8a shown in FIG.

FIG. 9 is a sectional view showing a state in which the inner layers of the two-layer coextrusion inflation film are adhered by blocking. In this figure, a two-layer coextrusion inflation film 8a is formed of an inner layer 1a and an outer layer 3a, and both are bonded by coextrusion. The inner layers 1a are also adhered to each other by blocking. Then, the laminated film is cut at a position indicated by an arrow in the drawing with a heating razor blade to produce the laminated film shown in FIGS.

10 to 16 show that the inner layer contains a thermoplastic resin having a Shore hardness lower than that of the outer layer thermoplastic resin,
FIG. 3 is a partial cross-sectional view showing a layer structure of an example of a laminated film in which an acid-modified polyolefin resin is contained in an inner layer and / or an inner layer.

The laminated film shown in FIG. 10 is a laminated film 14a in which a two-layer coextrusion inflation film 13a consisting of an inner layer 11a containing a light-shielding substance and an outer layer 12 is adhered by blocking the inner layers 11a to each other.

The laminated film shown in FIG. 11 is a two-layer coextrusion inflation film 13a consisting of an inner layer 11a containing a light-shielding substance and an outer layer 12a, and a laminated film 14a in which the inner layers 11a are adhered by blocking.

The laminated film shown in FIG. 12 is a laminated film in which the heat seal layer 15 is directly laminated on the laminated film 14a shown in FIG.

The laminated film shown in FIG. 13 is obtained by laminating a metal vapor-deposited flexible sheet layer 19 obtained by processing a metal vapor-deposited layer 17 into a heat-resistant flexible sheet 18 via an adhesive layer 16 on the laminated film 14a shown in FIG. It is a film.

The laminated film shown in FIG. 14 is a three-layer coextrusion inflation film 21a consisting of an inner layer 11a containing a light-shielding substance, an intermediate layer 20, and an outer layer 12, and a laminated film obtained by adhering the inner layers 11a to each other by blocking. 22a.

The laminated film shown in FIG. 15 is a laminated film obtained by laminating a heat seal layer 19 on the laminated film 22a shown in FIG. 14 with an adhesive layer 16a containing a light-shielding substance interposed therebetween.

The laminated film shown in FIG. 16 is a laminated film in which the heat resistant flexible sheet layer 18 is laminated on the laminated film 22a shown in FIG. 14 with the adhesive layer 16 interposed therebetween.

17 to 21 are partial plan views showing the shape of the strong adhesion portion of the laminated film. In the laminated film shown in FIG. 17, the strong adhesive portions 51 are formed in a scattered manner in the weak adhesive portions 52.

In the laminated film shown in FIG. 18, the strong adhesive portion 51 is formed in the weak adhesive portion 52 in a stripe shape in the vertical direction.

In the laminated film shown in FIG. 19, the strong adhesive portion 51 is formed in the weak adhesive portion 52 in a laterally streak shape.

In the laminated film shown in FIG. 20, the strong adhesive portions 51 are formed in the weak adhesive portions 52 in a lattice pattern.

In the laminated film shown in FIG. 21, the strong adhesive portion 51 is diagonally formed in the weak adhesive portion 52 in a stripe shape.

FIG. 22 is a schematic view showing a main part of an apparatus for producing a laminated film having a multilayer structure in which the inner surfaces of an inflation film are adhered by blocking.

In this figure, reference numeral 34 is a central reversing roll for reversing the cut central laminated film, and reference numeral 35 is a side reversing roll for reversing the cut lateral laminated film. Then, a central part winding shaft 36 is provided on the central part reversing roll 34 side, and a side part winding shaft 37 is provided on the side part reversing roll 35 side.

Further, between the pressure roll (nip roll) 33 and the central reversing roll 34, there are provided heat cutting blades 38, 38 which are blades of a safety razor for cutting the laminated film. 38 is provided with heating means 39 for heating the heating cutting blade 38. An ion spraying device 40 for removing static electricity from the laminated film is provided near the heating cutting blade 38.

In order to produce a laminated film with the above-mentioned apparatus, for example, a layer which is weakly blocked and adhered while the pressure roll (nip roll) 33 is heated by the heating means 39 to the Vicat softening point of the inner layer or higher. The film base material 41 is fed. Then, the laminated film substrate 41 is pressed by the pressure roll 33.
Then, the inner surfaces are blocked and adhered to each other.
The laminated film base material 41 is sent to a cutting blade 38 and cut into three rolls to produce a central roll-shaped laminated film 43 and both side roll-shaped laminated films 44, 44. Since 38 is heated by the heating means to a temperature above the softening point of the inner layer of the laminated film, it is in a melt-bonded state in the vicinity of the cut surface which is the cut portion of the laminated film.

Since the ions are blown by the ion blowing device 40 before and after the cutting, static electricity is removed.

Laminated film 4 produced in this way
3, 44, 44, the central laminated film 43 is wound around the central winding shaft 36 through the central reversing roll 34 and the winding core, and the lateral laminated films 44, 44 are It is wound around a side winding shaft 37 via a partial reversing roll 35 via a winding core.

The heating temperature of the heating cutting blade 38 is preferably the above-mentioned example, but can be set within the range of 50 ° C. or higher and the melting point of the laminated film or lower.

The method of cutting the laminated film base material is not limited to the above-mentioned example, and the following method can be used. (1) Cut the film with a fixed blade and a heating rotary blade (for example, JP-A-64-58492) (2) Cut with a heating rotary blade. (3) A laser beam is applied to melt and cut. (4) Melt and cut with flame (slit shape).

Since it is excellent in various necessary characteristics such as low cost, suitability for film slit, large electric resistance and easy heat generation,
A safety razor blade is preferred. Further, since the cutting edge of the cut object is melted by the heat of the cutting tool, generation of cutting chips is eliminated.

The means for removing static electricity is not limited to the above-mentioned example, and a corona discharge device is used, or a knitted fabric, a woven fabric, a non-woven fabric or the like using a conductive fiber such as a metal molding, a conductive film, a metal fiber or a carbon fiber is used. The static electricity generated in the laminated film may be released by contacting the surface of the laminated film.

FIG. 23 shows a four-layer structure in which a two-layer coextrusion inflation film 9a (portion A) composed of an inner layer 1a and an outer layer 2 is formed by blocking adhesion between inner surfaces of the inner layer 1a by a pressure roll (nip roll). This is an apparatus for producing a laminated film 8a (portion B) laminated on.

Example 1 MI (measured value of ASTM D-1238 at 190 ° C.) was 1.2 g / 10 minutes, and density (A
STM D-1505 23 ° C measurement value) is 0.950g, Vicat softening point (A
STM D-1525) 123 ° C, Shore hardness (ASTM D-2240) 69
15% by weight of homopolyethylene resin of D, average particle size 21 mμ
Oil furnace carbon black of 2% by weight, monoglycerin ester 0.2% by weight, viscosity of 10,000 centistokes dimethylpolysiloxane 0.05% by weight, 5.8 Dimenthy
MI containing 2.1% by weight of l-tocotrienol 2.1g / 10min, density is
0.920g / cm ² , Shore hardness 55D, Vicat softening point 102
Thickness of ethylene / hexene-1 copolymer tree composition at ℃
20 μm outer layer, 3 wt% oil furnace carbon black with an average particle size of 21 mμ, 0.05 wt% dimethylpolysiloxane with a viscosity of 10,000 centistokes, 5.8 Dimenthy
l-tocotrienol 0.05% by weight, coumarone-indene resin 5
Ethylene butene with MI of 1.0% by weight, density of 0.89 g / cm ³ , Shore hardness of 38D, Vicat softening point of 75 ° C
-1 Two layers of 30 μm thick inner layer consisting of copolymer resin composition were coextruded to form a cylindrical tube film with blow ratio 1.4 using an inflation film molding machine, and an outer layer with far infrared lamp under the guide plate. The surface temperature is 40 ℃ ~ 70
After heating to ℃, squeeze squeeze roll (nip roll) of pressure roll to squeeze the inner layers, and then melt and cut with a razor heated to 80 ℃ due to electric resistance. To 50 cm
A sheet-shaped laminated film having a width of 3 Roll was prepared.

This laminated film has a moderate adhesive strength of 20 g / 15 mm width without peeling off the inner layers of the cut surface even during bag making, and has tear strength of 1600 g or more in both length and width, and gel gel test strength. It is more than 300 times, and it has almost no curling and is ideal as a light-shielding bag for heavy goods packaging.
Film with sharp edges (35mm x 3000ft roll)
Commercialized as a light-shielding bag for

[0166] Further, the cost is less than half that of a conventional laminated film in which 70 μm light-shielding LDPE film is laminated on both sides of a warrif with vertical adhesive layers, and it is rigid without curling, and dimethylpolysiloxane is used. Since it is included in the outer layer, the coefficient of friction of the film in a heated state can be reduced, and it is suitable for automatic bag making and heat sealing (for example, foreign matter sealing property, hot tack property, heat sealing strength, and temporal sealing strength)
It was a packaging material with excellent product insertion suitability.

Further, it was found that the combined use of dimethylpolysiloxane, carbon black, and 5.8 Dimenthy-tocotrienol significantly improved the light-shielding ability and the antioxidant ability due to the additive effect. Furthermore, even if dimethylpolysiloxane (viscosity 10,000 centistokes) is used as a lubricant, the dispersibility of carbon black is improved without adversely affecting the photographic performance, and the lubricity is improved. It was possible to reduce the friction coefficient of the laminated film in the heated state without generation, and it was possible to prevent wrinkles and deterioration of gloss during heat sealing during automatic bag making.

Example 2 MI of 1.1 g / 10 minutes, density of 0.954 g / cm ³ , Shore hardness of 69
D, homopolyethylene resin with Vicat softening point of 126 ° C 10
% Ethylene with MI 2.1 g / 10 min, density 0.920 g / cm ³ , Shore hardness 56 D, Vicat softening point 100 ° C.
Methylpentene-1 copolymer resin 87.65% by weight, viscosity 10,000 centistokes 0.05% by weight, 5.8 Dimenthyl-tocotrie
Inflation film molding using a polyolefin resin composition consisting of 0.1% by weight of nol, 2% by weight of oil furnace carbon black with an average particle size of 21 mμ, and 0.2% by weight of a nonionic antistatic agent (trade name: Electrostripper TS-2 manufactured by Kao Soap). Machine with blow ratio 1.2 and thickness 5
A single layer cylindrical tubular film with a thickness of 0 μm was created and crushed by a 50 mesh pressure mat roll (squeeze roll for take-up) heated to 100 ° C after passing through a guide plate to partially adhere the inner layers to each other. Made thickness 97μm
It is a laminated film consisting of two layers.

This laminated film has a tear strength of 1600 g or more and cannot be measured, the inner layer of the cut surface is not peeled off even during bag making, the gelbotest strength is 300 times or more, heat sealing suitability, bag making. The suitability, the product insertion suitability, etc. were excellent as in Example 1.

Comparative Example 1 The polyolefin resin composition of Example 2 had a viscosity of 10,000 centistokes of 0.05% by weight and a viscosity of 5.8 Dimenthyl-tocotrieno.
l 0.1% by weight is removed, and instead of the pressure mat roll heated to 100 ° C, the flat squeeze roll for crushing is used for crushing, and the film crushed into a flat plate is cut with a razor at room temperature. Although the inner layers did not adhere to each other, they could not be laminated films. In addition, the light-shielding property was insufficient, and light fog was slightly generated.

Example 3 The layer structure corresponds to FIG. The inner layer has a density of 0.92 g / cm ³ ,
MI 2.5g / 10min, Shore hardness 58D, Vicat softening point 98 ° C ethylene-octene-1 copolymer resin 75.8% by weight, density 0.94g / cm ³ , MI 2.4g / 10min, Shore hardness
(D) 35D, Vicat softening point 59 ℃, melting point 80 ℃ ethylene-vinyl acetate type acid-modified polyolefin resin 20
% By weight, average particle size 21 mμ, pH 7.7, oil fanace carbon black 3% by weight, calcium stearate
Made of a resin composition of 1.0% by weight, 0.1% by weight of phenolic antioxidant and 0.1% by weight of phosphorus antioxidant, thickness 25μ
m, Shore hardness is 52D, and Vicat softening point is 92 ° C.

The outer layer has a density of 0.92 g / cm ³ and MI of 2.1 g / 10
Min, Shore hardness 57D, Vicat softening point 100 ° C ethylene / 4 methylpentene-1 copolymer resin 71.7% by weight, density 0.96g / cm ³ , MI 6.5g / 10min, Shore hardness 72D,
Homopolyethylene resin with Vicat softening point of 126 ° C 10% by weight, density of 0.94 g / cm ³ , MI of 2.1 g / 10 minutes, Shore hardness of 63
D, 15% by weight of ethylene / 4 methylpentene-1 copolymer resin having a Vicat softening point of 118 ° C, average particle diameter of 21 mμ, pH
Oil fanace carbon black 3% by weight of 7.7,
Antistatic agent (Kao's trade name Electrostripper-TS
-2) The resin composition is 0.3% by weight, the thickness is 25 µm, the Shore hardness is 62D, and the Vicat softening point is 116 ° C.

The outer layer surface of the two-layer coextrusion inflation film having a total thickness of 50 μm consisting of the inner layer and the outer layer was air-cooled, and after the frost line was generated, it was reheated to 60 ° C. with a ring-shaped far infrared lamp at a position of 1.5 m. Heated. Then, the inner film is laminated by blocking adhesion without using an adhesive layer by a nip roll (pressure roll) essential for an inflation film forming machine, and is a laminated film having a vertically symmetrical four-layer structure with a thickness of 100 μm.

Example 4 The layer structure corresponds to that in FIG. The resin composition of the inner layer is the same as that of the inner layer of Example 3, and the thickness is 40 μm. The outer layer has a density of 0.94 g / cm ³ , MI of 1.3 g / 10 min, and Shore hardness (D) of 56.
D, Vicat softening point 100 ℃, melting point 120 ℃ L-LDPE type acid-modified polyolefin resin 20 wt%, nylon 66 resin (Asahi Kasei product name Leona) resin composition of 80 wt%, thickness 10μm, Rockwell hardness is 119R (ASTM D-
785), and the Vicat softening point is 198 ° C.

The outer layer surface of the two-layer coextrusion inflation film having a total thickness of 50 μm composed of the inner layer and the outer layer was air-cooled, and the inner layer was brought into contact with a water-cooled (cooling water 10 ° C.) mandrel to stabilize bubbles and then inflation. A laminated film having a vertically symmetrical four-layer structure in which inner layers are laminated by blocking adhesion with a nip roll essential to a film forming machine.

Example 5 The layer structure corresponds to that in FIG. The inner layer has a density of 0.94 g / c
m ^3, MI is 2.4 g / 10 min, Shore hardness (D) is 35D, Vicat softening point 59 ° C., a melting point of 80 ° C. Ethylene - instead of 30 wt% acid-modified polyolefin resin of vinyl acetate type, density 0.91g / cm ³ , MI 6.2g / 10min, Shore hardness (D) 46
D, Vicat softening point 91 ° C, melting point 112 ° C, L-LDPE type acid-modified polyolefin resin 30% by weight resin composition, thickness 25 μm, Shore hardness 55D, Vicat softening point 96 ° C, etc. Is the same as in Example 3.

Example 6 The layer structure corresponds to FIG. The inner layer has a density of 0.94 g / c
m ^3, MI is 2.4 g / 10 min, Shore hardness (D) is 35D, ethylene Vicat softening point 59 ° C. - instead of 30 wt% acid-modified polyolefin resin of vinyl acetate type, density 0.90 g / cm
³ , MI of 1.1g / 10min, Shore hardness (D) of 50D, Vicat softening point of 92 ° C, melting point of 110 ° C, LDPE type acid-modified polyolefin resin 30% by weight resin composition, thickness 25μ
m, Shore hardness 56D, Vicat softening point 97 ° C.

Example 7 The layer structure corresponds to FIG. The same blocking adhesive laminated film as in Example 3 and aluminum vacuum-deposited biaxially stretched polyester resin film having a thickness of 10 μm, Young's modulus of 218 kg / mm ² , and melting point of 260 ° C. were formed by vacuum-depositing aluminum in a thickness of 400 Å. MI was 9g / 10 at a thickness of 15μm prepared by extrusion lamination method at a resin temperature of 300 ℃.
Min, density 0.93 g / cm ³ , Shore hardness 53D, Vicat softening point 95 ° C, melting point 120 ° C 15% by weight of L-LDPE type acid-modified polyolefin resin, MI 7g / 10min, density 0.92
g / 10 minutes, a Shore hardness of 51 D, a Vicat softening point of 92 ° C. A polyolefin adhesive layer made of 85% by weight of a branched high-pressure branched homopolyethylene resin, and an aluminum vacuum deposition layer and an outer layer were adhered to each other 6 It is a laminated film having a layer structure.

Example 8 The layer structure is similar to that of FIG. Instead of aluminum vacuum-deposited biaxially stretched polyester resin film, the thickness is 1.5μ
m vinylidene chloride resin layer coated on both sides of a 20 μm thick biaxially oriented polypropylene resin film
Young's modulus called film is 210kg / mm ² , melting point is 120 ℃
The same as Example 7 except that the biaxially stretched film of No. 2 was used.

Example 9 The layer structure corresponds to FIG. Young's modulus of Example 7 is 218 k
Instead of aluminum vacuum-deposited biaxially stretched polyester resin film with g / mm ² and melting point of 260 ° C, aluminum vacuum-deposited biaxially stretched nylon resin film with thickness of 15 μm, Young's modulus of 246 kg / mm ² and melting point of 220 ° C is used. Other than that, it is the same as Example 7.

Example 10 The layer structure corresponds to FIG. The same block as in Example 4.
Ming 3.5g / 10min, density 0.9
3g / cm³, Shore hardness 53D, Vicat softening point 98 ℃, melting
L-LDPE type acid-modified polyolefin resin with a point of 120 ° C 1
0% by weight, MI 7g / 10min, density 0.92g / cm ³, Shore Hard
High pressure branched homopo with a degree of 51D and a Vicat softening point of 92 ° C
Polyethylene type acid-modified polyolefin resin 57 weight
%, MI 15g / 10 minutes, density 0.92g / cm ³, Shore hardness is 5
6D, Vicat softening point 105 ℃ ethylene / butene-1 co-weight
30% by weight of combined resin, average particle size of 21 mμ, pH of 7.7
Ilferness carbon black 3% by weight resin composition
A 30 μm thick light-shielding heat-sealing layer consisting of
Laminated by extrusion lamination method at 320 ℃ 5
It is a laminated film having a layer structure.

Comparative Example 2 The layer structure is similar to that of FIG. The inner layer of Example 3 as the outer layer,
A laminated film in which an inflation film having the same resin composition, thickness and the like is adhered by blocking except that the outer layer is arranged as the inner layer.

Comparative Example 3 The layer structure is similar to that of FIG. The outer layer is the same as the outer layer of Example 3, the inner layer has a density of 0.92 g / mm ³ , MI of 2.0 g / 10 minutes, has a Shore hardness of 57 D, and a Vicat softening point of 108 ° C. Polymer resin (DSM, Dutch company Stamilex) 96.9% by weight, oleic acid amide 0.1% by weight, average particle diameter 21mμ, pH 7.7 oil furnace carbon black 3% by weight, and thickness 25μm , A laminated film composed of two layers having a total thickness of 100 μm, in which inner layers are adhered to each other by blocking. Table 3 shows the results of comparing the characteristics of Examples 3 to 10 and Comparative Examples 2 and 3.

[0184]

[Table 3]

* 1: Figure 22: 3-sided heat-sealing bag automatic bag making with roll-shaped laminated film, both ends of which are slit by heating razor * 2: Sheet-shaped photo film 50 in the 3-sided heat-sealing bag
After sandwiching the sheet between cardboard U-shaped cardboard made of paperboard and sealing the bag, put it in a lid-fitting makeup box, and put this makeup box in 10 cardboard boxes Vibration test according to JIS Z-0322 Visual inspection of rear pinhole

[0186]

The present invention can prevent the laminated film adhered by blocking from peeling from the cut end portion,
No peeling, wrinkles, lines, swelling, etc. occur in the laminating process, bag making process, etc.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view of a laminated film of the present invention.

FIG. 2 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 3 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 4 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 5 is a partial sectional view of the laminated film of the present invention.

FIG. 6 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 7 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 8 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 9 is a schematic view showing a method for producing a laminated film of the present invention.

FIG. 10 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 11 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 12 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 13 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 14 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 15 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 16 is a partial cross-sectional view of the laminated film of the present invention.

FIG. 17 is a partial plan view showing the shape of a strong adhesion portion of the laminated film of the present invention.

FIG. 18 is a partial plan view showing the shape of the strong adhesion portion of the laminated film of the present invention.

FIG. 19 is a partial plan view showing the shape of the strong adhesion portion of the laminated film of the present invention.

FIG. 20 is a partial plan view showing the shape of the strong adhesion portion of the laminated film of the present invention.

FIG. 21 is a partial plan view showing the shape of the strong adhesion portion of the laminated film of the present invention.

FIG. 22 is a schematic diagram of a main part of a laminated film manufacturing apparatus of the present invention.

FIG. 23 is a schematic diagram of a main part of an apparatus for producing a laminated film having a four-layer structure by blocking adhesion using the two-layer coextrusion inflation film molding machine of the present invention.

[Explanation of symbols]

 1a ... inner layer 2 ... heat-melt adhesive part 3a ... outer layer 4 ... intermediate layer 5 ... adhesive layer 6 ... flexible sheet layer 7 ... heat seal layer 8a ... laminated film 9a ... two-layer coextrusion inflation film 10a ... three-layer coextrusion inflation Film 11a ... Inner layer 12, 12a ... Outer layer 13a, 21a ... Inflation film 14a, 22a ... Laminated film 15 ... Sheet seal layer 16, 16a ... Adhesive layer 17 ... Aluminum vapor deposition 18 ... Heat resistant flexible sheet 19 ... Aluminum vapor deposition flexible sheet layer 20 ... Intermediate layer a ... Indicates that a light-shielding substance is contained.

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[Procedure amendment]

[Submission date] December 26, 1991

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Correction target item name] Fig. 22

[Correction method] Change

[Correction content]

FIG. 22

[Procedure Amendment 2]

[Document name to be corrected] Drawing

[Correction target item name] Fig. 23

[Correction method] Change

[Correction content]

FIG. 23

Claims (10)

[Claims] 1. A laminated film in which the inner surface of an inflation film is adhered by blocking, wherein cut ends are heat-melted and adhered. 2. The inflation film has an outer layer,
The laminated film according to claim 1, which comprises an inner layer having a lower softening point (ASTM D-1525) than the outer layer. 3. The laminate according to claim 1, wherein a cylindrical film formed by an inflation film forming method is pressed flatly by a pressure roll to adhere it by blocking, and then cut by a melt cutting method. Film manufacturing method 4. A method for producing a laminated film, which comprises heating a surface of a cylindrical film formed by an inflation film forming method, and then pressing the film in a flat shape by a pressure roll to adhere the film by blocking. 5. A laminated film in which an inner surface of an inner layer of a multi-layer coextrusion inflation film having at least an inner layer and an outer layer is adhered by blocking, to the inner layer,
A laminated film characterized by containing a thermoplastic resin having a Shore hardness (ASTM D-2240) lower than that of the outer layer thermoplastic resin. 6. A multi-layer co-extrusion inflation film having at least an inner layer and an outer layer, wherein the inner surface of the inner layer is adhered by blocking, wherein the inner layer contains an acid-modified polyolefin resin. 7. The Vicat softening point (ASTM) of the outer layer is higher than that of the inner layer.
The laminated film according to any one of claims 1 to 6, which has a high D-1525) and a heat-sealing property. 8. Young's modulus (ASTM D-882) is 50 kg on the surface.
8. The laminated film according to claim 1, wherein flexible sheets having a heat resistance of / mm ² or more and heat resistance are laminated with or without an adhesive layer. 9. A Vicat softening point (ASTM
D-1525) is low, and a heat-sealable heat-sealing layer is laminated with or without an adhesive layer. 10. The cylindrical film formed by the inflation film forming method is non-planarly pressed by a pressure roll having a mold to adhere it by blocking with a weakened adhesive force. Process for producing laminated film described