JP2627591B2 - Laminated film and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art A laminated film in which a plurality of film layers are laminated is used as a packaging material used for packaging bags of photographic light-sensitive materials. To laminate the plurality of film layers, an adhesive layer is used. Or directly by the extrusion lamination method. However, a laminated film using such an adhesive or an extrusion lamination method not only requires a lot of laminating steps but also becomes expensive,
The curling was large and the adhesive strength was too large, and the layers were completely integrated and hardened, and the tear strength was low.

Therefore, the present inventor has proposed a laminated film that adheres in a somewhat flexible state by blocking without using an adhesive or an extrusion lamination method (Japanese Patent Application Laid-Open No. 64-22444).

[0004]

SUMMARY OF THE INVENTION The above-mentioned JP-A-64-22
The laminated film disclosed in Japanese Patent Publication No. 544 is extremely preferable because it has high tear strength, gelbo test strength, impact drilling strength, and the like, and does not cause curling. However, the adhesion due to blocking is unstable, and the adhesive may peel off from the cut end at a low temperature, or may be simulated by blocking in a laminating step or a bag making step when laminating another flexible sheet. In some cases, failures such as adhesion peeling, wrinkles, streaks, and swelling may occur, and this is a problem particularly in winter when the temperature is low or when cooling is strong.

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

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a laminated film adhered by blocking with appropriate strength which does not always peel off when manufactured under ordinary circumstances.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to achieve the above object, and 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. The cut end is characterized by being hot-melt bonded.

According to a third aspect of the present invention, there is provided a method for manufacturing a laminated film according to the present invention, wherein a cylindrical film formed by an inflation film forming method is pressed flat by a pressure roll and adhered by blocking, and then melt-cut. It is characterized in that it is cut at

According to a fourth aspect of the present invention, there is provided a method for manufacturing a laminated film according to the present invention, wherein a cylindrical film formed by an inflation film forming method is heated and then pressed flat by a pressure roll to adhere by blocking. It is characterized by doing.

The method of hot-melt bonding the cut ends of the laminated films bonded by blocking includes laser beam cutting, ultrasonic cutting, Flame (flame) cutting, discharge cutting, heating rotary blade cutting, and heating razor. There is a blade cutting method and the like. 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 is preferably the vigat softening point of the inner layer (ASTM D-152).
5) The temperature before and after is preferably 50 ° C. or higher and the melting point or lower, more preferably 70 to 150 ° C., and most preferably 80 to 120 ° C.

Preferable examples of the blocking adhesion include pressure bonding using a nip roll (pressure roll) (typical examples of the pressure bonding shape include planar pressing, dot pressing, and multiple vertical streaks. Press, grid press, multiple horizontal streak press, other various emboss press, etc.), sandwiched between a heated metal roll and an elastic roll such as a heat-resistant rubber roll or a cotton roll. Is carried out in a heated and pressurized state so as to form an adhesive shape. However, the present invention is not limited to the above representative examples.

As the metal roll, a roll having been subjected to various embossing irregularities may be used. As the shape of the emboss, for example, "Bearon Shibo" issued by Tokyo Bearon KK
Has been presented in more than 210 species. Also, even if the entire surface is adhered substantially uniformly in a planar shape, even if it is pressed in a non-planar shape, such as a dot, a line, a grid, a cloth, or the like, and partially adhered, the adhesive strength may be increased or decreased. Good.

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

Further, the heating temperature is preferably about the softening temperature of the inner surface of the blown film, since it is possible to obtain adhesion by blocking with appropriate strength 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 ° C or higher, preferably 50 to 140 ° C.
C., particularly preferably 60 to 120.degree.

The blown film may be a single layer or a multilayer coextruded film. In the case of a single-layer blown film, it is necessary to make a difference between the inner surface and the outer surface of the film. As the method, for example, a temperature difference is provided by a ring die, or a temperature difference is provided by air cooling only the outer surface of the film.

The resin used in the multilayer co-extrusion blown film having two or more layers is preferably different between the inner layer to be blocked and the outer layer not to be blocked. The resin used for the inner layer has a low softening point and excellent physical strength. Preferred are ethylene copolymer resins, propylene copolymer resins, tackifiers and polyolefin-modified resins. Preferred ethylene copolymer resins for the inner layer are shown below.

Representative 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, referred to as
(Indicated 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 metal such as zinc Resin) (12) Ethylene-α-olefin copolymer resin (L-LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin

[0018] Among the ethylene copolymer resins, L-LDPE resin and EE have good film moldability and heat sealability, and have high bag breaking strength, impact hole punching strength and tear strength.
A resin is preferred.

It is also preferable to use a blend with other thermoplastic resins, various elastomers, various rubbers, various additives and modifiers in order to meet the required properties.

Among the ethylene copolymer resins, particularly preferred is an ethylene / α-olefin copolymer resin, which is generally referred to as a linear low-density polyethylene resin (hereinafter abbreviated as L-LDPE resin). It is.

[0021] L-LDPE (L iner L ow D enaity P oly e tyiene)
The resin is referred to as a third polyethylene resin, and is a low-cost, high-strength resin that meets the needs of the era of energy saving and resource saving combining the advantages of both the medium-low pressure method and the high pressure method polyethylene resin. This resin is obtained by low-pressure method or high-pressure improvement method by using ethylene and α-alkyl having 3 to 13, preferably 4 to 10 carbon atoms.
It is a copolymer of olefins and is a polyethylene resin having a linear linear structure with short branches. Preferred α-olefins in terms of physical strength and cost include butene-1, octene-1, hexene-1, 4-methylpentene-1,
Heptene-1 and the like are used.

The density is generally about the same as that of a low- to 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 within 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 improvement apparatus.

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

Specific examples of the L-LDPE resin are shown below. Ethylene-butene-1 copolymer resin G resin and NUC-FLX (UCC) Dourex (Dow Chemical) Screa (DuPont Canada) Marlex (Philips) Stamilex (DSM) Exelen VL (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Yuka) Nisseki Linirex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene / hexene-1 copolymer resin TUFLIN ( UCC) TUFTHENE (Nihon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultoxex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical) Screa ( DuPont Canada ) MORETEC (Idemitsu Petrochemical)

A particularly preferred representative example is given by a trade name, wherein polyethylene has 6 carbon atoms as an α-olefin side chain.
Of 4-Methylpentene-1 introduced by Mitsui Petrochemical Co., Ltd.
MORETEC of Idemitsu Petrochemical Co., Ltd.
And DSM's Stamirex and Dow Chemical's Dourex (these are L-LDPE resins obtained by a liquid phase process with four companies). Preferable representative examples obtained by the gas phase process of the low-pressure method are listed as trade names. TUFLIN and UCC of Nippon Unicar Co., Ltd., in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. TUFTHENE and others.

Further, recently released ultra low density linear low density polyethylene resin having a density of less than 0.910 g / cm ³ , for example, U
NUC-FLX of CC Company and Excelen V of Sumitomo Chemical Co., Ltd.
L is also preferable (both two products use butene-1 having 4 carbon atoms in the α-olefin).

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

[0029]

[Table 1]

Also, since it is a polyolefin resin having a low degree of polymerization, tackification of polyolefin resin having an average molecular weight of 300 to 7000, rosin resin, terpene phenol resin, petroleum resin, coumarone indene resin, styrene resin, phenol resin, etc. A thermoplastic resin containing an agent, particularly various polyolefin resins including a tackifier and a low-polymerization degree polyolefin resin, is preferable for ensuring blocking adhesion. It is preferable to contain a total of at least 50% by weight of one or more of these resins. 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 by 5 ° C. or more than the outer layer is excellent in stable blocking adhesion and physical strength. This is preferred because a laminated film can be obtained.

As the resin used for the outer layer, a resin having a Vicat softening point higher than that of the inner layer by 5 ° C. or more and excellent in blown film moldability, physical strength and heat sealability is preferable. For example, the density is 0.920 g / cm 3. ² or more ethylene / α-olefin copolymer resin, density 0.920g / cm ³
The above homopolyethylene resin, homopolypropylene resin, propylene / α-olefin copolymer resin, polyamide resin such as nylon 6, nylon 66, nylon 11, nylon 12, etc. (including copolymer resin with other resins), polyester resin And a blended resin in which the total of one or more of the above-mentioned resins is 50% by weight or more. Particularly, 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 heat sealability, α-olefin copolymer resins having 2 to 6 carbon atoms are preferred, ethylene / α-olefin copolymer resins are particularly preferred, and ethylene and α-olefin copolymer resins are most preferred. 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 securing the heat sealing strength over time. is there. By forming the outer layer of an inflation film using a resin composition containing 15% by weight of an ethylene / α-olefin copolymer resin, it is possible to provide a packaging bag excellent in heat seal strength over time, hot tack property, and physical strength. .

It is preferable to add carbon black, metal powder (including paste), carbon fiber, conductive polymer, metal fiber, antistatic agent and lubricant to the inflation film for the purpose of improving the antistatic property.

Examples of the most preferable classification of carbon black as the light-shielding substance include gas black, furnace black, channel black, anthracene black, acetylene black, ketjen carbon black, thermal black, lamp black, oil smoke, pine smoke, Animal black, vegetable black and the like.
In the present invention, furnace carbon black is preferable for the purpose of improving light-shielding properties, cost, and physical properties.As an expensive light-shielding substance having an antistatic effect, acetylene carbon black and Ketjen carbon black, which is a modified by-product carbon black, are preferred. . If necessary, it is also preferable to mix the former and the latter according to required characteristics. There are various forms of blending a light-shielding substance into a polyethylene polymer, such as dry color, liquid color, paste color, master batch pellets, compound color pellets, granular color pellets, etc.The master batch method using master batch pellets Is preferable in terms of cost, prevention of contamination of the work place, and the like. Japanese Patent Publication No. 40-26196
No. 3-10362 describes a method of preparing a polymer-carbon black masterbatch by dispersing carbon black in a solution of a polymer dissolved in an organic solvent. It describes how to make a batch. The present inventor has also proposed a resin composition for a colored masterbatch in JP-A-63-186740.

When the laminated film of the present invention is used as a packaging bag for photosensitive material, no fogging occurs, there is little change in the sensitivity of the photosensitive material, the light-shielding ability is large, and L-LDPE is used.
Even when added to a resin film, it is hard to generate carbon black hardening (fuzziness) and foreign matter that generates pinholes in the film such as fish eyes. Diameter 10 ~
120 mμ, volatile components 2.0% or less, cyanide and sulfur components 1.0% or less, preferably 0.5% or less, particularly preferably
Furnace carbon black having an oil absorption of not more than 0.1% and an oil absorption of not less than 50 ml / 100 g is preferred. The channel carbon black is expensive and often causes fog on the photographic material (particularly, sulfur component), which is not preferable. Even if it must be used, the effect on photographic properties should be investigated and the type and amount added should be selected.

Preferable carbon black products that can be used particularly for packaging materials for photosensitive materials whose quality is deteriorated by oxidation / reduction substances include, for example, carbon black # 20 (B) and # 20 manufactured by Mitsubishi Kasei. 30 (B), # 33
(B), # 40 (B), # 44 (B), # 45 (B), # 50, # 55, # 10
0, # 600, # 2200 (B), # 2400 (B), MA8, MA11, M
A100 and the like.

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

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

As the carbon fiber, there are carbon fiber, silicon carbide fiber and the like. It has the effect of improving conductivity and physical properties, but is expensive.

Examples of the metal fiber include a brass fiber and a stainless steel fiber. Although the conductivity is improved, the specific gravity increases and the cost is high.

In any case, when used for packaging materials for photosensitive materials (especially when used on the photosensitive material side), the total amount of sulfur and cyanide is 1.0% or less, preferably 0.5% or less, particularly preferably 0.1% or less. % Is preferable in order not to deteriorate the photographic properties (fog, sensitivity, gradation, color balance, etc.) of the photosensitive material.

Representative examples of the antistatic agent used in the present invention are described below. I. Nonionic (= nonionic) (1) Alkylamine derivatives: T-B103 (Matsumoto Yushi), T-B1
04 (Matsumoto Yushi) Alkylamide type polyoxyethylene alkylamine: Armostat 31
0 (lion fat) Tertiary amine (lauryl amine): Armostat 400 (lion fat) N, N-bis (2-hydroxyethyl cocoamine): Armostat
410 (lion fat) 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), Eliq SM-2 (Yoshimura Oil Chemical) Oxalic acid-N, N'-distearylamide butyl ester: Hoechst poly Oxyethylene alkyl amide (3) Ether type Polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nH Polyoxyethylene alkyl phenyl ether Special non-ion type: Register 104, PE100, 116-118
(Daiichi Kogyo Pharmaceutical Co., Ltd.), Resistat PE132, 139 (Daiichi Kogyo Pharmaceutical Co., Ltd.), Elegan E115, Chemistat 1005 (Nippon Yushi), Erik BM-1 (Yoshimura Oil Chemical), Electrostripper TS, TS2, 3, 5, EA, EA2, 3 (Kao soap) (4) Polyhydric alcohol ester type glycerin fatty acid ester: Monogly ((Nippon camphor), TB
-123 (Matsumoto Yushi), Resistat 113 (Daiichi Kogyo Pharmaceutical) Sorbitan fatty acid ester Special ester: Elique BS-1 (Yoshimura Oil Chemical) 1-Hydroxyethyl-2-dodecylglyoxazoline: British cellophane

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

III. Cationic (1) Amide-type cation: Resist PE300, 401, 402,
406, 411 (Daiichi Kogyo Seiyaku) (2) Quaternary ammonium salt quaternary ammonium chloride quaternary ammonium sulfate quaternary ammonium nitrate Katimine CSM-9 (Yoshimura Oil Chemical), CATANAC 609 (American cyanamide), Denon 314C (Marubishi Yuka), Armostat 300 (Lion Fat), 100V (Armor), Electro Stripper-ES (Kao Soap), Chemistat 20
09A (Nippon Yushi) Stearamido propyl-dimethyl-β-hydroxyethyl ammoniu
m nitrate: CATANAC / SN (American dianamid)

IV. Zwitterionic (1) Alkyl petane type: (2) Imidazoline type: Rheostat 53, 532 (lion oil and fat), AMS 53 (lion oil and fat), AMS 303, 313 (lion oil and fat) Alkyl imidazoline type (3) Metal salt: AMS 576 (by Lion Yushi) rheostat 826, 923 (by Lion _{Yushi) (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 Polyvinyl benzyl type cation Polyacrylic acid type cation

VI. Others: Registerat 204, 205 (Daiichi Kogyo Pharmaceutical), Elegan 2E, 100E (Nippon Yushi), Chemistat 1002, 1003, 2010 (Nippon Yushi), Elique 51
(Yoshimura Oil Chemical), ALROMINE RV-100 (Geigy)

[0048] Among the above antistatic agents, nonionic (nonionic) antistatic agents are particularly preferred because of their small adverse effect on photographic properties and human body.

The antistatic agent will be specifically described. As the internal antistatic agent used by mixing in the thermoplastic resin, any of a nonionic type, an anionic type and an amphoteric type may be used.

Specific examples of the nonionic compounds include ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkylphenols, and esters (eg, esters of higher fatty acids and polyhydric alcohols, polyethylene glycol glycols of higher fatty acids, etc.). ), Polyethers and amides (eg, higher fatty acid amides, dialkylamides, ethylene oxide adducts of higher fatty acid amides, etc.) are effective.

Examples of the anionic system include alkyl allyl phosphonic acid, adipic acid, glutamic acid, alkyl sulfonates, alkyl sulfate, polyoxyethylene alkyl phosphate, fatty acid salt, alkyl benzene sulfonate, alkyl naphthalene sulfonate, and sodium dialkyl. Sulfosuccinate is effective.

Examples of the cationic system include amines (eg, alkylamine phosphate, Schiff base, amidoamine, polyethyleneimine, complex of amidoamine and metal salt, alkylester of amino acid, etc.), imidazolines, amine-ethylene oxide adduct And quaternary ammonium salts.

As for the amphoteric 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 preferred.

Inorganic electrolytes, metal powders, metal oxides, kaolins, silicates, carbon powders, and carbon fibers, which fall outside the above categories, also have the effect of the present invention. Further, graft polymerization and polymer blending are also effective.

Representative examples of the antistatic agent for external use include polyhydric alcohols (eg, glycerin, sorbite, polyethylene glycol, polyethylene oxide, etc.), polyhydric alcohol esters, and higher alcohol ethylene in the case of nonionics. -Oxide adducts, alkylphenol ethylene oxide adducts,
There are fatty acid ethylene oxide adducts, amides, amide oxide ethylene adducts, amine oxide ethylene adducts, and the like. In amphoteric systems, carboxylic acids (eg, alkylalanine, etc.) and sulfonic acids are effective. .

In the anionic system, a carboxylate, a sulfuric acid derivative (for example, an alkyl sulfonate, etc.) and a phosphoric acid derivative (for example, phosphonic acid, a phosphate, etc.) polyester derivative are preferred.

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

The names of typical commercial lubricants and the names of manufacturers added to the polyolefin resin film layer of the present invention are described below.

(1) Silicone oil lubricant; various grades of dimethylpolysiloxane and its modified products (Shin-Etsu Silicone, Toray Silicone), polymethylphenylsiloxane, olefin-modified silicone, polyether-modified silicone modified with polyethylene glycol or polypropylene glycol And silicone oils containing modified siloxane bonds such as olefin / polyether-modified silicon, epoxy-modified silicon, amino-modified silicon, and alcohol-modified silicon. In the silicone oil,
In particular, olefin-modified silicon, polyether-modified silicon, and olefin / polyether-modified silicon are excellent. The silicone oil improves the coefficient of friction of the film in the heated state, reduces the sliding resistance that occurs during sealing of the hot plate by the automatic wrapping machine, and prevents wrinkles from occurring, resulting in a beautiful appearance and high sealing performance. And a basis for obtaining a film which retains the performance of having good adhesion to the packaged object. In addition, a beautiful seal portion can be obtained by preventing a decrease in gloss due to sliding. In the present invention in which a silicon-based oil is used in combination, the coefficient of high-temperature friction can be reduced to 1.4 or less when performing sliding heat sealing.

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

The effects of the addition of a silicon-based oil are many for the use of the present invention as follows. The surface of these materials is coated and improved in dispersibility only by being used in combination with the fibrous filler, the non-fibrous light-shielding substance, and the pigment. Improves resin fluidity, reduces screw motor load, and prevents melt fracture. The lubricity can be sufficiently ensured without adding a fatty acid amide that bleeds out to form a white powder. The coefficient of friction of the film in the heated state can be reduced, the suitability for automatic bag making can be improved, wrinkles during heat sealing and gloss reduction due to sliding can be prevented, and a beautiful sealed portion can be obtained. When used in combination with a light-shielding substance, the light-shielding ability can be improved, and the light-shielding property can be ensured even when the physical properties are improved by reducing the amount of the light-shielding substance that decreases the physical properties. (2-1) Fatty acid amide-based lubricant; (2-1) Saturated fatty acid amide-based lubricant Behenic acid amide-based lubricant; Diamid KN (Nippon Kasei), etc. Stearamide-based lubricant; Armide HT (Lion fat), Alflow S-10 ( Nippon Yushi), 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-based lubricant Erucamide amide-based lubricant; Alflow P-10 (Nippon Oil & Fats), 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) Bis fatty acid amide lubricant Henamide amide-based lubricant; Diamid NK bis (Nippon Kasei), etc. Methylene bisstearic amide-based lubricant; Diamid 200 bis (Nippon Kasei), Armowax (Lion
Akzo), bisamide (Nitto Kagaku), etc. Methylene bisoleic amide lubricant; Lubron O
(Nippon Kasei) etc. Ethylene bisstearic amide lubricant; Armoslip EBS (Lion Akzo), etc. Hexamethylene bisstearic amide lubricant; Amide 65 (Kawaken Fine Chemical), etc. Hexamethylene bis oleamide amide lubricant; Amide 60 (Kawaken Fine Chemical), etc. (2-4) Monoalkylolamide lubricant N- (2-hydroxyethyl) lauric amide lubricant;
N- (2-hydroxyethyl) stearamide amide-based lubricants such as Tohoru N130 (Toho Kagaku); N- (2-hydroxymethyl) stearamide amide-based lubricants such as amizole (Kawaken Fine Chemical); methylolamide (Nitto Chemical) etc. 3) Nonionic surfactant lubricant; electro stripper
-TS-2, electro stripper-TS-3 (Kao soap), etc. (4) Hydrocarbon lubricants; liquid paraffin, natural paraffin, microwax, synthetic paraffin, polyethylene wax, polypropylene wax, chlorinated hydrocarbon,
Fluorocarboxylate (5) fatty acid lubricants; higher fatty acids (C ₁₂ or higher is preferable), hydroxy fatty acid (6) ester lubricant; lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty fatty acid Alcohol esters (7) alcohol-based lubricants; polyhydric alcohols, polyglycols, polyglycerols (8) metallic soaps; higher fatty acids such as lauric acid, stearic acid, ricinoleic acid, naphthenic acid, 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 having a large lubricating effect and easy to bleed out, the amount is reduced to 0.01 to 1.0% by weight, and Is preferable.

The laminated film of the present invention comprises various photosensitive materials,
Food, pharmaceuticals, dyes, resins, concentrated products, fishmeal, fertilizers, cement, explosives, etc., various packaging bags, product cover films, multi-films for agricultural chemicals, waterproof films, moisture-proof films, light-proof films, cold-proof films, heat-resistant films, etc. It can be used for packaging materials and the like.

On the other hand, considering the case of landfill treatment as waste, it is only necessary to use a degradable plastic which is currently under study or is partially introduced into the market. For example, as a biodegradable polymer, IC
"BIOPOL" by Company I, "Polycaprolactone" by UCC or a polymer that is indirectly disintegrated by blending natural or synthetic polymers that are susceptible to biodegradation as additives, or starch blending heat A plastic resin, for example, various ethylene copolymer resins, various polyethylene resins, and the like can also be used.

It is also possible to use a photodegradable polymer. For example, use is made of an ECO copolymer obtained by copolymerizing ethylene and carbon monoxide in which a carbonyl group has been introduced as a photosensitizing group into the main chain during the polymerization of polyethylene, or a transition metal salt, an oxidation accelerator, a photosensitizer as an additive. A material having photodegradability can be used by adding a material or the like to the base polymer.

Typical examples of the light-sensitive material are shown below. (a) Silver halide photographic material (X-ray photographic film, printing film (lith film), black and white and color photographic paper, color film, printing master paper, DTR photographic material, computerized photosetting film and paper, microfilm, movie (B) diazonium photographic material (4-morpholinobenzenediazonium microfilm, microfilm,
(C) Photosensitive materials containing azide and diazide-based photographic materials (para-azide benzoate, 4,4'diazide stilbene, etc.)
(E.g., copying films, printing plates, etc.) (d) Quinonediazide-based photographic materials (orthoquinonediazide, orthonaphthoquinonediazide compounds such as benzoquinone (1,2) -diazide- (2) -4-sulfonic acid phenyl ether, etc.) A photosensitive material containing, for example, a printing plate material,
(E) Photopolymer (photosensitive material containing vinyl-based monomer, printing plate, adhesive film, etc.) (f) Polyvinylcinnamic acid ester (for example, printing film, IC) (Resist, etc.) In addition, photosensitive materials that are altered or degraded by various kinds of light, oxygen, sulfur dioxide, etc., such as foods (butter, peanuts, margarine, snack products, knobs, confectionery, tea, glue, etc.), medical products (gastrointestinal drugs, It is also applicable to packaging of powdered or granular medicines such as case medicines), ABS resins, dyes, pigments, photographic developing chemicals, photographic fixing chemicals, and toner.

The packaging form applied to the packaging material for photographic light-sensitive materials using the laminated film of the present invention includes a single flat bag,
Double flat bag, free standing bag, single gusset bag, double gusset bag,
In addition to packaging pouches such as standing pouches and handbags, there are also laminated films, moisture-proof boxes, light-blocking light-blocking magazines, magazine-less light-blocking light-blocking members, and leader paper. The bag is formed by a conventionally known plastic film bonding method such as a hot plate bonding method, an impulse bonding method, a fusing bonding method, an ultrasonic bonding method, and a high frequency bonding method. In addition,
It is also possible to make a bag by an adhesive method using an adhesive or an adhesive, or an adhesive method using a pressure-sensitive or heat-sensitive adhesive.

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 comprising an inner layer and an outer layer is adhered by blocking, the inner layer has a shore hardness (thermoplastic) higher than that of the thermoplastic resin of the outer layer. (ASTMD-2240).

Furthermore, the laminated film of the present invention according to claim 6 is a laminated film in which the inner surface of an inner layer of an inflation film composed of an inner layer and an outer layer is adhered by blocking, wherein the inner layer contains an acid-modified polyolefin resin. It is configured as a feature.

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 ensuring adhesion by blocking, flexibility and gelbo test strength. And it is preferable that it is 2D or more, especially 5D or more lower than the Shore hardness of the thermoplastic resin contained in the outer layer.

The above thermoplastic resins 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 an unsaturated carboxylic acid. Examples thereof include a graft-modified polyethylene resin, a graft-modified resin, an ethylene / ethyl acrylate copolymer resin, and a 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. Preferred is a graft-modified polyolefin resin obtained by grafting an unsaturated carboxylic acid such as acrylic acid, maleic acid, or maleic anhydride to a polyolefin resin.

The graft ratio of unsaturated carboxylic acids is 0.01
It is preferably about 10%. Unsaturated carboxylic acids are
It is a generic term including its derivatives, and typical examples include 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, monoethyl maleate, diethyl maleate,
Fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid diethyl ester, acrylic acid amide,
Methacrylamide, maleic monoamide, maleic 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-monobutylamide, fumaric acid-N, N-dibutylamide,
Maleimide, monomethyl maleate, dimethyl maleate, potassium methacrylate, sodium acrylate, zinc acrylate, magnesium acrylate, calcium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, N-butylmaleimide, N-phenyl Maleimide, maleenyl chloride, glycidyl maleate, dipropyl maleate, aconitic anhydride, sorbic acid and the like can be mentioned, and they can be mixed with each other. Among these, acrylic acid, maleic acid, maleic anhydride and nadic acid are preferred, and maleic anhydride is particularly preferred.

The method for graft-modifying unsaturated carboxylic acids in the acid-modified polyolefin resin is not particularly limited. For example, reacting in the molten state
No. 1, the method disclosed in JP-B-44-15422, which reacts in a solution state, the method disclosed in JP-B-43-18144, etc., which reacts in a slurry state,
There is a method disclosed in Japanese Patent Publication No. 50-77493 for reacting 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 the unsaturated carboxylic acids used is determined based on the polyolefin resin base polymer (various polyethylene resins, various polypropylene resins, various polyolefin copolymer resins, polybutene-1 resin, poly-4-methylpentene-1) in order to secure the adhesive strength. 0.01 to 20 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of α-olefin resin such as resin.
Parts by weight are preferred.

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

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, α, α ′
Bis (t-butylperoxydiisopropyl) benzene, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane,
2,5-dimethyl-2,5-di (t-butylperoxy) hexine, di-t-butyl peroxide, cumene hydroperoxide, t-butyl-hydroperoxide, dicumyl peroxide, t-butyl peroxide Oxylaurate, t-
Butylperoxybenzoate, 1,3 bis (t-butylperoxyisopropyl) benzene, cumene hydroperoxide, di-t-butyl-diperoxyphthalate,
t-butyl peroxymaleic acid, isopropyl percarbonate and the like. 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 ° C.
Di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5-di (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 may be 0.005 to 100 parts by weight of the polyolefin resin.
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 Kogyo KK “Novatech-AP” Mitsubishi Yuka KK “MODIC” Nippon Unicar KK “NUC-ACE”

Examples of the polyolefin resin include a polyethylene resin, an ethylene copolymer resin, a polypropylene resin, a propylene copolymer resin, and a vinyl chloride resin. In particular, an ethylene copolymer resin is preferable since heat suitability, bag breaking strength, and impact piercing strength are improved.

Although the above-mentioned acid-modified polyolefin resin is contained in the inner layer, the content is preferably from 5 to 80% by weight, particularly preferably from 10 to 60% by weight. If the content is less than 5% by weight, not only is it difficult to always cause adhesion by blocking over the entire inner surface of the inner layer, but also 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, and it is difficult to put into practical use. When the content exceeds 80% by weight, adhesion due to blocking can be caused over the entire surface, and the effect of improving the dispersibility of the light-shielding substance can be increased. Is deteriorated, and becomes expensive and is difficult to put to practical use.

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

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

The resin used for the outer layer includes various thermoplastic resins and various elastomers. It is necessary to select a resin having higher antiblocking property, abrasion resistance, Shore hardness and Vicat softening point than the inner layer. Heat-sealing applications, such as laminated films used for bags, need to have heat-sealing properties, and when used for photographic photosensitive materials, select a resin that does not adversely affect photographic performance. There is a need. When heat sealability is required, various polyolefin resins having a 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. Preferred are various polyester resins, high molecular weight polyethylene resins, and high molecular weight polypropylene resins.

The shore hardness of the resin used for the outer layer as described above is 2D higher than the shore hardness of the resin used for the inner layer.
Above, preferably 5D or higher. In terms of Shore hardness, it is 50D or more, preferably 60D or more, particularly preferably 70D or more. In any case, the resin is higher than the inner layer by 2D or more in difference from the Shore hardness.

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 sealing properties.

The Vicat softening point of the outer layer should be equal to or higher than the Vicat softening point of the inner layer. Suitability for heat sealing at the time of bag making (appearance, prevention of pinholes and breakage due to melting of outer layer, prevention of strength reduction, etc.) In particular, especially 5 ° C
It is preferable that the temperature is higher than the Vicat softening point of the inner layer. Prevents excellent appearance and physical strength of the heat-sealed part,
In order to improve the bag making speed, it is preferable that the temperature is higher by at least 10 ° C. than the Vicat softening point of the inner layer.

The laminated film of the present invention according to claim 8 comprises:
The surface has a Young's modulus (ASTM D-882) of 50 kg / mm ² or more and heat resistance (a flexible sheet such as paper, cellophane, cloth, etc. having a melting point of 100 ° C. or more or having no melting point is said to have heat resistance in the present invention). The laminated film is obtained by laminating with or without interposing an adhesive layer and a laminated film to which a cut end portion in which the inner surface of the flexible sheet is adhered by blocking is hot-melted.

Examples of the flexible sheet laminated on the surface include thermoplastic resin films such as various polyethylene resins, ethylene copolymer resins, polypropylene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyamide resins, polycarbonate resins, and polyester resins. Known films, modified resin films thereof, and uniaxially or biaxially stretched films. Further, cellulose acetate film, cellophane, regenerated cellulose film, ethylene / vinyl alcohol copolymer resin film (Eval resin film), paper, synthetic paper, nonwoven fabric, and the like may be used.

Particularly preferred flexible sheets are various types of papers having a basis weight of 20 to 400 g / m ² (unbleached kraft paper, semi-bleached kraft paper, Bleached kraft paper, high yield pulp paper, neutral paper,
Hineri base paper, clupak paper, duostress 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 a pigment layer, coating of a resin layer, metal deposition, etc.), and may be colored in various colors. In order to impart light-shielding properties, various light-shielding substances may be added, or paper coated on the surface may be used, and various types of molding may be applied as necessary.

[0093] Other preferable heat-resistant flexible sheets include a biaxially stretched thermoplastic resin film and cellophane. For some applications, a uniaxially stretched thermoplastic resin film is also preferred.

The biaxially stretched thermoplastic resin film can be obtained by a 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. As the thermoplastic resin used for this film, 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 And a tertiary or higher copolymer resin.The copolymer may be a random copolymer or a 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 polyester resins include resins synthesized from dimethyl terephthalate and ethylene glycol, dimethyl terephthalate and 1,4-cyclohexanehexane, dimethyl terephthalate and dimethyl isophthalate. Nylon 6, Nylon 66, Nylon 12, Nylon 11, Nylon 6 for various polyamide resins
-66 copolymer resin and the like.

These resins are biaxially stretched by a T-die film forming machine or an inflation film forming machine to form a film.

The surface of the uniaxially or biaxially stretched thermoplastic resin film and the cellophane may be subjected to metal deposition, coating of a vinylidene chloride resin layer, or the like, or may be subjected to various printings or coloring to various colors. Good. The surface may be subjected to various types of molding for the purpose of improving lubricity and improving printability.

The thickness of the biaxially stretched thermoplastic resin film is preferably from 5 to 70 μm, particularly preferably from 7 to 50 μm, more preferably from 7 to 50 μm, in order to reduce the thickness of the packaging material, reduce costs, and ensure flexibility and physical strength. 35 μm is most preferred. 5μ thick
If it is less than m, wrinkles and cuts are likely to occur in the laminating process, and if it exceeds 70 μm, the rigidity is too large, the suitability for bag making is deteriorated, and the gelbo test strength and handleability are deteriorated, and it becomes expensive.

The flexible sheet has a Young's modulus (ASTM
D-882) is preferably high, and is 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. The heat resistance is preferably 50 ° C. or more, more preferably 10 ° C. or more than that of the outer layer to be heat-sealed from the viewpoint of improving bag making suitability and improving appearance. It is preferable to have

The Young's modulus (AS) laminated on the surface of claim 8
TM D-882) is 50 kg / mm ² or more, preferably 80 kg / mm ² or more,
Particularly preferred examples of the heat-resistant flexible sheet of 100 kg / mm ² or more are shown below.

Flexible sheet name Young's modulus (kg / mm ² ) Melting point (° C.) Biaxially oriented high-density polyethylene film 80-90 137 Unoriented polypropylene film 60-90 140 Biaxially oriented polypropylene film 150-350 175 Vinylidene chloride coat 2 Axial stretched polypropylene film 170-260 175 Biaxially stretched polyamide film 130-280 225 Biaxially stretched polyester film 190-400 260 Cellophane 140-210 150 (carbonized) Vinylidene chloride coated 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 formed by a commonly used wet lamination method, dry lamination method, hot melt lamination method, extrusion lamination method, coextrusion extrusion lamination method, or the like. Although it can be used, various thermoplastic resins having a small amount of volatile substances which easily affect the photographic light-sensitive material, 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 strength to the heat-resistant support cannot be secured. When the thickness exceeds 50 μm, not only the cost becomes high but also the neck-in becomes large.

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

As the resin used for the heat sealing layer, there are various thermoplastic resins having heat sealing properties, but various polyolefin resins are preferable, and low density homopolyethylene resin and various ethylene copolymer resins are particularly preferable. Representative examples of particularly preferred 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, referred to as
(Indicated 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 metal such as zinc (Resin) (12) Ethylene-α olefin copolymer resin (L-LDPE resin) (13) Ethylene-propylene-butene-1 terpolymer resin In the ethylene copolymer resin, film moldability and heat sealing suitability L-LDPE resin and EEA resin are preferred because they have good bag breaking strength, impact puncture strength and tear strength.

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

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

[0109] L-LDPE (L iner L ow D enaity P oly e tyiene)
The resin is referred to as a third polyethylene resin, and is a low-cost, high-strength resin that meets the needs of the era of energy saving and resource saving combining the advantages of both the medium-low pressure method and the high pressure method polyethylene resin. This resin is obtained by low-pressure method or high-pressure improvement method by using ethylene and α-alkyl having 3 to 13, preferably 4 to 10 carbon atoms.
It is a copolymer of olefins and is a polyethylene resin having a linear linear structure with short branches. Preferred α-olefins in terms of physical strength and cost include butene-1, octene-1, hexene-1, 4-methylpentene-1,
Heptene-1 and the like are used.

The density is generally about the same as that of 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 within the range of 0 minutes.

Examples of the polymerization process of the L-LDPE resin include a gas phase method using a medium / low pressure apparatus, a liquid phase method, and an ionic polymerization method using a high pressure improvement apparatus.

Among these L-LDPE resins, particularly preferred in view of physical strength, heat seal strength and film moldability are those having a melt index (hereinafter referred to as MI) of 0.8 to 1;
0g / 10min (measured at 190 ° C according to ASTM D-1238), density 0.870 ~
0.940 g / cm < ³ > (measured at 23 [deg.] C. according to ASTM D-1505) and obtained by a liquid phase process and a gas phase process having 6 to 8 carbon atoms of an α-olefin.

Specific examples of the L-LDPE resin are shown below. Ethylene-butene-1 copolymer resin G resin and NUC-FLX (UCC) Dourex (Dow Chemical) Screer (DuPont Canada) Marlex (Philips) Stamilex (DSM) Exelen VL (Sumitomo Chemical) Neozex (Mitsui Petrochemical) Mitsubishi Polyethylene-LL (Mitsubishi Yuka) Nisseki Linirex (Nippon Petrochemical) NUC Polyethylene-LL (Nippon Unicar) Idemitsu Polyethylene L (Idemitsu Petrochemical) Ethylene / hexene-1 copolymer resin TUFLIN ( UCC) TUFTHENE (Nihon Unicar) Ethylene / 4-methylpentene-1 copolymer resin Ultoxex (Mitsui Petrochemical) Ethylene / octene-1 copolymer resin Stamirex (DSM) Dourex (Dow Chemical) Screa ( DuPont Canada ) MORETEC (Idemitsu Petrochemical)

A particularly preferred representative example is given by a trade name, wherein polyethylene has 6 carbon atoms as an α-olefin side chain.
Of 4-Methylpentene-1 introduced by Mitsui Petrochemical Co., Ltd.
MORETEC of Idemitsu Petrochemical Co., Ltd.
And DSM's Stamirex and Dow Chemical's Dourex (these are L-LDPE resins obtained by a liquid phase process with four companies). Preferred representative examples obtained by the low-pressure gas-phase process are listed below under trade names. TUFLIN and UCC of Nippon Unicar Co., Ltd., in which hexene-1 having 6 carbon atoms is introduced as an α-olefin side chain. TUFTHENE and others.

Further, recently released ultra low density linear low density polyethylene resin having a density of less than 0.910 g / cm ³ , for example, U
NUC-FLX of CC Company and Excelen V of Sumitomo Chemical Co., Ltd.
L is also preferable (both two products use butene-1 having 4 carbon atoms in the α-olefin).

[0116] The EEA resin is, for example, Union Carbide (USA), Nippon Unicar Co., Ltd., Mitsubishi Yuka Co., Ltd., Sumitomo Chemical Co., Ltd., Mitsui Polychemicals Co., Ltd., etc. as representative manufacturers. . As specific examples, representative brand names of EEA resins currently marketed by Nippon Unicar Co., Ltd. and their comonomer content, melt index, and density are shown (comonomer content: 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 a decrease in heat seal strength over time.

According to a tenth aspect of the present invention, there is provided a method for producing a laminated film according to the present invention, wherein a pressure-sensitive roll formed by molding a cylindrical film formed by an inflation film forming method is pressed non-planarly so that the adhesive strength is reduced. The cutting end of the laminated film adhered by the above method is hot-melt bonded.

The embossing may be performed in the form of a dot, a plurality of warp streaks, a lattice, a plurality of weft streaks, a texture, or various other shapes (for example, a typical embossed shape is “Bearon Shibo” issued by Tokyo Bearlon KK). (More than one type of metal roll) that has been embossed (heating or room temperature may be performed, but heating is preferable because blocking adhesion is stable. The heating temperature is below the melting point, and around the softening point. (Preferably) and an elastic roll such as a heat-resistant rubber roll or a cotton roll, and passed under pressure (heated if necessary).

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

[0122]

According to a first aspect of the present invention, there is provided a laminated film in which an inner surface of an inflation film is adhered by blocking, and in a laminated film whose cut end is heat-melted, the hot-melt adhesive portion is an inner layer. They are firmly fixed to each other to prevent the inner layers from peeling off.

In the method for producing a laminated film according to the third aspect of the present invention, a cylindrical film formed by an inflation film forming method is pressed flat by a pressure roll, adhered by blocking, and then melt-cut by a cutting method. By cutting, the hot-melt bonded portion is firmly fixed and the inner layers are prevented from peeling off from each other.

In the method for producing a laminated film according to the present invention, a cylindrical film formed by an inflation film forming method is heated and then pressed flat by a pressure roll to adhere by blocking. In the method for producing a laminated film, the blocking adhesion is improved by heating before pressing with a pressure roll.

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 has a heat resistance lower than the thermoplastic resin of the outer layer. Since a plastic resin is contained, the inner layers are firmly adhered to each other.

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

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 a heat sealing property, so that the inner layer is heated and heated so that the inner layers are firmly adhered to each other. There is no pinhole even when pressurized, and the suitability for bag making is improved without impairing the appearance.

The laminated film of the present invention according to claim 8 has a heat-resistant flexible sheet laminated on its surface with a Young's modulus of 50 kg / mm ² or more, so that the heat-sealing suitability is improved and the heat-sealing property is improved. It prevents pinholes, improves wear resistance and impact resistance, and keeps the appearance beautiful. Further, the adhesion between the inner layers is strengthened so as not to peel off. Further, the laminated film of the present invention according to claim 9 has a Vicat softening point lower than that of the outer layer and a heat sealable heat seal layer laminated on the surface to be heat sealed, so that heat seal sealing can be performed at a low temperature. , Preventing occurrence of pinholes and deterioration of appearance.

Further, in the method for manufacturing a laminated film according to the present invention, a cylindrical film formed by an inflation film forming method is pressed non-planarly by a press roll formed with a mold to impart strength to the adhesive force. Adhesion by blocking also improves blocking adhesion between inner surfaces.

[0130]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the laminated film of the present invention will be described with reference to the drawings. 1 to 8 are partial cross-sectional views showing a layer structure of a laminated film of the present invention in which a cut end is 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-adhering it, and cutting only one of the films to form two layers. The laminated film 8a overlaps the inner layer 1a at the cut end face. A hot-melt bonding portion 2 is formed at the portion, and the inner layers 1a are securely fixed to each other.

The laminated film 8a shown in FIG. 2 is a two-layer co-extruded inflation film comprising an inner layer 1a and an outer layer 3a.
9a is folded back and subjected to blocking bonding, and only one is cut to form four layers, and the hot-melt bonded part 2 is formed in the same region where the inner layer 1a overlaps.

In the laminated film 8a shown in FIG. 3, a three-layer co-extruded inflation film 10a composed of an inner layer 1a, an intermediate layer 4 and an outer layer 3a was folded and blocked and bonded, and only one was cut to form six layers. Stuff, inner layer
In the overlapping portion of 1a, the hot-melt bonding portion 2 is formed similarly.

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

The laminated film 8a shown in FIG. 5 is a two-layer co-extruded blown film composed of an inner layer 1a and an outer layer 3a.
9a is folded back and subjected to blocking bonding, and both ends are cut to form a four-layer structure. The overlapping portion of the inner layer 1a is similarly formed with the hot-melt bonding portion 2.

In the laminated film 8a shown in FIG. 6, a three-layer co-extruded inflation film 10a composed of an inner layer 1a, an intermediate layer 4 and an outer layer 3a was folded and blocked and bonded, and both ends were cut to form six layers. The inner layer 1a
The hot-melt bonding portion 2 is formed in the same region.

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

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 a two-layer co-extruded blown film are adhered to each other by blocking. In this figure, a two-layer co-extrusion blown film 8a is formed of an inner layer 1a and an outer layer 3a, and both are adhered by co-extrusion. The inner layers 1a are also adhered to each other by blocking. Then, the film is cut by a heating razor blade at a position indicated by an arrow in the figure, and a laminated film shown in FIGS. 2 and 5 is prepared.

FIGS. 10 to 16 show that the inner layer contains a thermoplastic resin having a lower Shore hardness than the thermoplastic resin of the outer layer.
FIG. 4 is a partial cross-sectional view illustrating a layer configuration of an example of a laminated film in which an acid-modified polyolefin resin is contained in an inner layer.

The laminated film shown in FIG. 10 is a laminated film 14a in which a two-layer co-extruded inflation film 13a composed of an inner layer 11a containing a light-shielding substance and an outer layer 12 is bonded by blocking the inner layers 11a.

The laminated film shown in FIG. 11 is a laminated film 14a in which a two-layer co-extruded inflation film 13a comprising an inner layer 11a containing a light-shielding substance and an outer layer 12a is bonded to each other by blocking the inner layers 11a.

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 of FIG.

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

The laminated film shown in FIG. 14 has a three-layer co-extruded blown film 21a including an inner layer 11a containing a light-shielding substance, an intermediate layer 20, and an outer layer 12, and the inner layers 11a are adhered to each other by a block. 22a.

The laminated film shown in FIG. 15 is a laminated film in which a heat seal layer 19 is laminated on a laminated film 22a shown in FIG. 14 via an adhesive layer 16a containing a light-shielding substance.

The laminated film shown in FIG. 16 is a laminated film obtained by laminating a heat-resistant flexible sheet layer 18 via an adhesive layer 16 on a laminated film 22a shown in FIG.

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

In the laminated film shown in FIG. 18, the strong bonding portion 51 is formed in the weak bonding portion 52 in a streak 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 the form of a horizontal stripe.

In the laminated film shown in FIG. 20, a strong bonding portion 51 is formed in a lattice shape in a weak bonding portion 52.

In the laminated film shown in FIG. 21, a strong bonding portion 51 is formed in a diagonal streak shape in a weak bonding portion 52.

FIG. 22 is a schematic view showing a main part of an apparatus for manufacturing a multilayer film having a multilayer structure in which the inner surfaces of an inflation film are blocked and adhered to each other.

In this figure, reference numeral 34 denotes a center reversing roll for reversing the cut center laminated film, and reference numeral 35 denotes a side reversing roll for reversing the cut side laminated film. A center winding shaft 36 is provided on the center reversing roll 34 side, and a side winding shaft 37 is provided on the side reversing roll 35 side.

Further, between the pressure roll (nip roll) 33 and the center reversing roll 34, there are provided heating cutting blades 38, 38 which are blades of a safety razor for cutting the laminated film. The heating device 39 for heating the heating cutting blade 38 is provided on the heating blade 38. In the vicinity of the heating cutting blade 38, an ion spraying device 40 for removing static electricity from the laminated film is provided.

In order to manufacture a laminated film using the above-described apparatus, for example, first, a heating roll 39 is used to heat the pressure roll (nip roll) 33 to a temperature higher than the Vicat softening point of the inner layer, and the film is weakly laminated and bonded. The film substrate 41 is fed. Then, the laminated film substrate 41 is
And the inner surfaces are bonded by blocking.
The laminated film substrate 41 is sent to a cutting blade 38 and cut into three rolls to produce a rolled laminated film 43 at the center and rolled laminated films 44 on both sides. 38 is heated to a temperature higher than the softening point of the inner layer of the laminated film by the heating means, and is in a melt-bonded state in the vicinity of the cut surface, which is the cut portion of the laminated film.

In addition, since ions are sprayed by the ion spraying device 40 before and after cutting, static electricity is removed.

The thus-produced laminated film 4
3, 44, and 44, the central laminated film 43 is wound around a central winding shaft 36 via a central reversing roll 34 via a winding core, and the lateral laminated films 44, 44 are It is wound around a side winding shaft 37 via a winding core through a part reversing roll 35.

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

The method of cutting the laminated film substrate is not limited to the above-mentioned example, but can be performed by the following method. (1) The film is cut with a fixed blade and a heated rotary blade (for example, Japanese Patent Application Laid-Open No. 64-58492). (2) The film is cut with a heated rotary blade. (3) Melt and cut by applying a laser beam. (4) Melt and cut with flame (slit shape).

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 cut edge of the object to be cut is melted by the heat of the blade, the generation of chips is eliminated.

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

FIG. 23 shows a two-layer co-extruded inflation film 9a (part A) composed of the inner layer 1a and the outer layer 2 formed of four layers by blocking adhesion between the inner surfaces of the inner layer 1a using a pressure roll (nip roll). This is an apparatus for manufacturing a laminated film 8a (part B).

Example 1 MI (measured at 190 ° C. of ASTM D-1238) was 1.2 g / 10 min, and density (A
0.950 g of STM D-1505 measured at 23 ℃, Vicat softening point (A
STM D-1525) is 123 ℃, Shore hardness (ASTM D-2240) is 69
15% by weight of homopolyethylene resin of D, average particle diameter 21mμ
2% by weight of oil furnace carbon black, 0.2% by weight of monoglycerin ester, 0.05% by weight of dimethylpolysiloxane having a viscosity of 10,000 centistokes, 5.8 Dimenthy
l-tocotrienol containing 0.1wt% MI 2.1g / 10min, density
0.920 g / cm ² , Shore hardness 55D, Vicat softening point 102
Thickness composed of ethylene-hexene-1 copolymer tree composition at ℃
20 μm outer layer, 3% by weight of oil furnace carbon black having an average particle diameter of 21 μm, 0.05% by weight of dimethylpolysiloxane having a viscosity of 10,000 centistokes, 5.8 Dimenthy
l-tocotrienol 0.05% by weight, cumarone-indene resin 5
Ethylene butene with MI of 1.0 g / 10 min, density of 0.89 g / cm ³ , Shore hardness of 38 D, Vicat softening point of 75 ° C containing weight%
-1 Co-extrusion of 30 μm thick inner layer made of copolymer resin composition to make cylindrical tube film with blow ratio of 1.4 using blown film molding machine, and outer layer with far infrared lamp just below guide plate The surface temperature is 40 ℃ ~ 70
C., and the inner layers are bonded by crushing with a squeeze roll (nip roll) for taking off a pressure roll, and then melt-cut with a razor heated to 80.degree. C. by electric resistance, as shown in FIG. To 50cm
Three rolls of a sheet-like laminated film having a width were prepared.

[0165] This laminated film did not peel off the inner layers of the cut surface even during bag making, had an appropriate adhesive strength of 20 g / 15 mm width, had a tear strength of 1600 g or more in both the vertical and horizontal directions, and had a gelbotest strength. More than 300 times, with almost no curling, ideal as a light-shielding bag for packing heavy goods,
Movie film with sharp edges (35mm x 3000ft roll)
Practical use as a light-shielding bag.

Also, the cost is less than half compared to a conventional laminated film in which a 70 μm light-shielding LDPE film is laminated with a vertical streak-like adhesive layer on both sides of a warifu, has no curling, is rigid, and has dimethylpolysiloxane. Since it is included in the outer layer, the coefficient of friction of the film in the heated state can be reduced, and suitability for automatic bag making and suitability for heat sealing (such as foreign matter sealing property, hot tack property, heat sealing strength, temporal sealing strength, etc.)
It was a packaging material with excellent product insertability.

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 surplus effect. Furthermore, even when dimethylpolysiloxane (viscosity of 10,000 centistokes) is used as a lubricant, dispersibility of carbon black is improved without adversely affecting photographic performance, lubricity is improved, and white powder due to bleed-out like fatty acid amide is used. It was possible to reduce the coefficient of friction of the laminated film in the heated state without generation, and to prevent the occurrence of wrinkles and reduction in gloss during heat sealing during automatic bag making.

Example 2 MI: 1.1 g / 10 min, density: 0.954 g / cm ³ , Shore hardness: 69
D, homopolyethylene resin 10 having a Vicat softening point of 126 ° C
% By weight, ethylene 2.1 with MI 2.1 g / 10 min, density 0.920 g / cm ³ , Shore hardness 56D, Vicat softening point 100 ° C
87.65% by weight of methylpentene-1 copolymer resin, 0.05% by weight of viscosity of 10,000 centistokes, 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 having an average particle diameter of 21mμ, and 0.2% by weight of a nonionic antistatic agent (trade name: Electrostripper TS-2 manufactured by Kao Soap) With a blow ratio of 1.2 and a thickness of 5
A single-layer cylindrical tubular film with a thickness of 0 μm is made, crushed by a 50-mesh pressure mat roll (take-off squeeze roll) heated to 100 ° C after passing through a guide plate, and the inner layers are partially strongly bonded. 97μm thickness
This is a laminated film having two layers.

[0169] The laminated film had no tearing of the inner layers of the cut surface during the bag making, had a tear strength of 1600 g or more, was unmeasurable, had a gelbo test strength of 300 times or more, and was suitable for heat sealing and bag making. The suitability, suitability for product insertion, 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 5.8 Dimenthyl-tocotrieno.
l Remove 0.1% by weight and crush it with a commonly used flat take-off squeeze roll instead of a pressure mat roll heated to 100 ° C, and cut the flat-plate crushed film with a razor at room temperature. However, the inner layers did not adhere to each other, and a laminated film could not be obtained. In addition, the light-shielding property was insufficient and light fog was slightly generated.

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

The outer layer has a density of 0.92 g / cm ³ and an MI of 2.1 g / 10
Min, a Shore hardness of 57D, -1 co ethylene 4-methylpentene Vicat softening point of 100 ° C. polymeric resin 71.7 wt%, a density of 0.96 g / cm ^3, MI is 6.5 g / 10 min, Shore hardness 72D,
10% by weight of homopolyethylene resin with Vicat softening point of 126 ° C, density of 0.94 g / cm ³ , MI of 2.1 g / 10 min, Shore hardness of 63
D, 15% by weight of ethylene / 4-methylpentene-1 copolymer resin having a Vicat softening point of 118 ° C., an average particle size of 21 μm, and a pH
3% by weight of oil fanace carbon black of 7.7,
Antistatic agent (Product name: Electro Stripper TS manufactured by Kao)
-2) A resin composition of 0.3% by weight, a thickness of 25 µm, a Shore hardness of 62D, and a Vicat softening point of 116 ° C.

The outer layer surface of a two-layer co-extruded blown film having a total thickness of 50 μm comprising the inner layer and the outer layer was air-cooled, and after a frost line was generated, the temperature was raised to 60 ° C. with a ring-shaped far-infrared lamp at a position of 1.5 m. Heated. The inner layer is laminated by blocking adhesion without using an adhesive layer by a nip roll (pressure roll) essential for an inflation film forming machine.

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

The surface of the outer layer of the two-layer co-extruded inflation film having a total thickness of 50 μm, comprising 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 the bubbles. This is a vertically symmetrical four-layer laminated film in which inner layers are laminated by blocking adhesion using a nip roll essential for a film forming machine.

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

Example 6 The layer configuration corresponds to FIG. 0.94g / c density in inner layer
m ³ , MI 2.4 g / 10 min, Shore hardness (D) 35D, Vicat softening point 59 ° C. Instead of 30% by weight of an acid-modified polyolefin resin of an ethylene-vinyl acetate type, the density is 0.90 g / cm.
^3. An LDPE-type acid-modified polyolefin resin having an MI of 1.1 g / 10 min, a Shore hardness (D) of 50 D, a Vicat softening point of 92 ° C. and a melting point of 110 ° C., and a resin composition of 30% by weight, and a thickness of 25 μm.
m, Shore hardness is 56D and Vicat softening point is 97 ° C, except that it is the same as Example 3.

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

Example 8 The layer configuration is similar to that of FIG. 1.5μ thickness instead of aluminum vacuum deposited biaxially stretched polyester resin film
m of vinylidene chloride resin layer applied to both sides of a biaxially oriented polypropylene resin film having a thickness of 20 μm.
The film has a Young's modulus of 210 kg / mm ² and a melting point of 120 ° C
This example is the same as Example 7 except that the biaxially stretched film was used.

Example 9 The layer configuration corresponds to FIG. Young's modulus of Example 7 is 218k
g / mm ^2, use instead of melting point 260 ° C. Aluminum vacuum deposited biaxially oriented polyester film, thickness 15 [mu] m, Young's modulus 246 kg / mm ^2, the aluminum vacuum deposition biaxially stretched nylon resin film having a melting point of 220 ° C. The rest is the same as the seventh embodiment.

Example 10 The layer configuration corresponds to FIG. The same block as in Example 4.
3.5g / 10min, density 0.9
3g / cm^Three, Shore hardness 53D, Vicat softening point 98 ° C, 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 ^Three, Shore Hard
Degree of 51D, Vicat softening point of 92 ° C
57% by weight of ethylene-modified acid-modified polyolefin resin
%, MI is 15g / 10min, density is 0.92g / cm ^Three, Shore hardness is 5
6D, ethylene-butene-1 co-weight with Vicat softening point of 105 ℃
30% by weight of coalescing resin, average particle size 21mμ, pH 7.7
Is the resin composition of il furnace carbon black 3% by weight?
30 μm thick light-shielding heat seal layer
5 laminated by extrusion lamination at 320 ° C
It is a laminated film having a layer configuration.

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

Comparative Example 3 The layer configuration is similar to FIG. The outer layer is the same as the outer layer of Example 3, and the inner layer has a density of 0.92 g / mm ³ , an MI of 2.0 g / 10 min, a Shore hardness of 57D, and a Vicat softening point of 108 ° C., which is commercially available ethylene octene-1. 96.9% by weight of polymer resin (trade name: Stamirex, DSM, Netherlands), 0.1% by weight of oleamide, 3% by weight of oil furnace carbon black having an average particle diameter of 21mμ and a pH of 7.7, and a thickness of 25μm This is a laminated film composed of two layers having a total thickness of 100 μm in which the 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: Fig. 22 Roll-shaped laminated film slit at both ends with a heated razor, 3-side heat seal bag automatic bag making * 2: Sheet-like photographic film 50 on the above 3-side heat seal bag
After sandwiching the sheets between cardboard U-shaped cardboards and sealing the bag, put them in a lid-fitting decorative box, and put this decorative box in 10 boxes of cardboard.Vibration test according to JIS Z-0322 Visual inspection of rear pinhole

[0186]

According to the present invention, the laminated film adhered by blocking can be prevented from peeling off from the cut end,
No peeling, wrinkling, streaking, swelling, etc. occur in the laminating step, the bag making step and the like.

[Brief description of the 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 cross-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 a shape of a strongly bonded portion of the laminated film of the present invention.

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

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

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

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

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

FIG. 23 is a schematic view of a main part of an apparatus for producing a four-layer laminated film by blocking adhesion using a two-layer co-extrusion blown film forming machine of the present invention.

[Explanation of symbols]

 1a ... Inner layer 2 ... Hot fusion bonding part 3a ... Outer layer 4 ... Intermediate layer 5 ... Adhesive layer 6 ... Flexible sheet layer 7 ... Heat seal layer 8a ... Laminated film 9a ... Two-layer co-extrusion blown film 10a ... Three-layer co-extrusion 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 it contains a light-shielding substance.

Claims (10)

(57) [Claims] 1. A laminated film in which an inner surface of an inflation film is adhered by blocking, wherein a cut end of the laminated film is heat-melted. 2. An inflation film comprising: an outer layer;
2. The laminated film according to claim 1, comprising an inner layer having a lower softening point (ASTM D-1525) than the outer layer. 3. The lamination according to claim 1, wherein the cylindrical film formed by the inflation film forming method is pressed in a plane by a pressure roll, adhered by blocking, and then cut by a melt cutting method. Film manufacturing method 4. A method for producing a laminated film, comprising heating a surface of a cylindrical film formed by an inflation film forming method, pressing the surface in a plane with a pressure roll, and bonding by blocking. 5. A laminated film in which an inner surface of an inner layer of a multilayer co-extruded inflation film having at least an inner layer and an outer layer is adhered by blocking,
Laminated film characterized by containing a thermoplastic resin having a lower Shore hardness (ASTM D-2240) than the thermoplastic resin of the outer layer 6. A multilayer film in which an inner surface of an inner layer of a multilayer co-extruded inflation film having at least an inner layer and an outer layer is bonded by blocking, wherein the inner layer contains an acid-modified polyolefin resin. 7. The outer layer has a higher Vicat softening point (ASTM) than the inner layer.
The laminated film according to any one of claims 1 to 6, wherein D-1525) is high and has heat sealability. 8. The surface has a Young's modulus (ASTM D-882) of 50 kg.
laminated film according to / mm ² or more, and to the heat resistance of the flexible sheet claims 1 are stacked without via or through the adhesive layer 7 9. On the surface, a Vicat softening point (ASTM
The laminated film according to any one of claims 1 to 8, wherein the heat-sealable layer having a low D-1525) and being heat-sealable is laminated with or without an adhesive layer. 10. The method according to claim 1, wherein the cylindrical film formed by the inflation film forming method is non-planarly pressed by a molded pressure roll and adhered by blocking with an increased or decreased adhesive force. Method for producing a laminated film as described above