JP5145912B2 - Laminated film for packaging and packaging bag - Google Patents

Description

  The present invention relates to a laminated film for packaging and a packaging bag.

Conventionally, in a laminated film for packaging, an aluminum vapor-deposited film having a light-shielding function or an aluminum laminate is used as a protective measure for package contents, particularly for preventing oxidation of fats and oils. However, the use of aluminum could develop into plastic and metal segregation issues and recycling and environmental issues.
As a light-shielding packaging material having a low environmental load related to waste found in aluminum packaging materials and having a barrier property and a light shielding property, a transparent barrier film having a gas barrier property from the outside, a printing ink layer, and a heat sealing resin layer are provided. A light-shielding packaging material that is laminated in order is known (see Patent Document 1).
In addition, at least one layer uses a rutile type titanium oxide as a white pigment in a multilayer laminated film including a light-shielding propylene-based resin layer made of a resin composition containing a propylene-based resin as a main component and further containing a black pigment and a white pigment. It is known (see Patent Document 2).
However, the light-shielding packaging material described in Patent Document 1 is filled with the contents in a packaging bag using this light-shielding packaging material, subjected to retort processing after sealing, and subjected to storage evaluation. May pour out the pigment containing the printing ink layer and cause abnormal odor.
Moreover, in the packaging bag which consists of a multilayer laminated film of patent document 2, the fats and oils of the contents will contact the rutile type titanium oxide used as a pigment through a sealant, and odor abnormalities resulting from the pigment will occur. There is.
JP 2000-280394 A JP 2005-225210 A (refer to claim 11)

  SUMMARY OF THE INVENTION An object of the present invention is to provide a laminated film for packaging and a packaging bag that does not cause abnormal odor when the packaging bag containing the contents is filled and sealed, and the sealed packaging bag containing the contents is heated and sterilized. Is to provide.

Invention of Claim 1 solves the subject regarding said laminated film for packaging, In the laminated film for packaging which consists of a base film and a multilayer unstretched olefin sealant, the said multilayer unstretched olefin sealant is comprised. At least one of the layers is a white colored layer formed by kneading and forming a polyolefin, a white pigment and a pigment dispersant, and the white pigment covers the surface of rutile titanium, rutile titanium, SiO ₂ , Al _The gist of the present invention is a laminated film for packaging, comprising a surface treatment agent comprising ₂ O ₃ and a polyol.

In the laminated film for packaging of the present invention, at least one of the layers constituting the multilayer unstretched olefin sealant is a white colored layer formed by kneading a polyolefin, a white pigment and a pigment dispersant, and the white pigment is a rutile type. Since it includes a surface treatment agent composed of titanium, rutile titanium and SiO ₂ , Al ₂ O ₃ and a polyol, it has a hydrophilic effect due to the hydrophilic group imparting effect, making SiO ₂ stronger than rutile titanium. Because the SiO ₂ layer adheres and blocks the oil and fat content of the contents in the packaging bag, the photo-oxidation reaction of the rutile titanium causes deterioration of the oil and fat in contact with the rutile titanium, resulting in an abnormal odor. It is prevented.
In the present invention, the white colored layer imparts cosmetic appearance to the laminated film for packaging.
The laminated film for packaging of the present invention can be used particularly for packaging retort foods, snacks, fats and oils, frozen foods and the like.

In the present invention, the ratio of rutile type titanium, SiO ₂ , Al ₂ O ₃ and polyol in the white pigment is as follows: rutile type titanium (pure component): 90 to 95 wt%, SiO ₂ : 3.5 to 5.0 wt%, Al ₂ O ₃ : 2.0 to 3.5 wt%, polyol: 0 to 1.0 wt% are preferable.

  In the present invention, the white colored layer is preferably composed of polyolefin: 69 to 95 wt%, white pigment: 4 to 30 wt%, and pigment dispersant: 0.001 to 1.0 wt%.

In the laminated film for packaging of the present invention, a gray shading layer formed by kneading and molding a polyolefin, a white pigment and a black pigment is laminated adjacent to the white colored layer and on the side opposite to the base film. May be.
The white pigment is composed of rutile titanium and a surface treatment agent composed of SiO ₂ , Al ₂ O ₃ and a polyol which covers the surface of the rutile titanium particles.
Rutile titanium ratio of SiO _2, Al ₂ O ₃ and polyols, rutile titanium _{(purity): 90~95wt%, SiO 2:} 3.5~5.0wt%, Al 2 O 3: 2.0 It is preferable that it is -3.5 wt% and polyol: 0-1.0 wt%.
In this embodiment, the content of the white pigment is 5 to 30 times that of the black pigment.
Further, iron black, graphite, or carbon black can be used as the black pigment, and benzpyrene-free carbon black having a benzpyrene concentration of 5 ppb or less that avoids the incorporation of benzpyrene, which has been pointed out as carcinogenic in recent years, is particularly preferable.
The gray light shielding layer prevents transmission of sunlight, fluorescence, or the like, and prevents the contents from being decomposed or altered, or from fading or other light deterioration.
Similarly to the case of the white colored layer, the white pigment contained in the gray light-shielding layer is a surface treatment agent comprising rutile titanium, rutile titanium, and a surface treatment agent comprising SiO ₂ , Al ₂ O ₃ and a polyol. Because of this, SiO ₂ that has a hydrophilic effect due to the hydrophilic group imparting effect adheres firmly to rutile titanium, and the SiO ₂ layer blocks the oil and fat content in the packaging bag made of this laminated film for packaging. Therefore, the photo-oxidation reaction of rutile type titanium prevents deterioration of the oil and fat in contact with the rutile type titanium, thereby preventing an abnormal smell.

  In the present invention, a second white colored layer may be further laminated adjacent to the gray light shielding layer. As a result, it is possible to further enhance the effect of preventing the transmission of sunlight, fluorescence, or the like, decomposing or altering the contents, or preventing the occurrence of light deterioration such as fading.

In the present invention, a black light shielding layer can be laminated instead of the gray light shielding layer. This black light shielding layer is formed by kneading and molding polyolefin and a black pigment. As the black pigment constituting the black light-shielding layer, iron black, graphite or carbon black can be used. In particular, benzpyrene-free carbon black having a benzpyrene concentration of 5 ppb or less that avoids the incorporation of benzpyrene, which has been pointed out as carcinogenic in recent years. Is preferred.
Since the black light-shielding layer completely shields light, this embodiment has extremely excellent utility as a packaging material for photosensitive materials as industrial members that require complete light-shielding. Does not generate harmful substances, etc., and is extremely excellent in disposal and environmental suitability.

  In the present invention, the polyolefin constituting each layer of the multilayer unstretched olefin sealant is polypropylene, propylene-ethylenepropylene rubber block copolymer, propylene-ethylene random copolymer, high-pressure method low-density polyethylene, ethylene-α-olefin copolymer. , Medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, or a combination of two or more of the above olefins.

  Claim 10 solves the problem relating to the packaging bag, and the summary of the packaging bag is the laminated film for packaging according to any one of claims 1 to 9. The packaging bag made of the laminated film for packaging of the present invention, particularly the retort packaging bag, does not change the odor of the contents even after retort sterilization, and can sufficiently withstand long-term storage. .

The laminated film for packaging of the present invention comprises a base film and a multilayer unstretched olefin sealant, and at least one layer constituting the multilayer unstretched olefin sealant is kneaded and molded with a polyolefin, a white pigment and a pigment dispersant. The white colored layer gives the cosmetic appearance to the laminated film for packaging, and the contents are decomposed or altered, or the occurrence of fading or other light deterioration is prevented.
Further, since the white pigment includes a surface treatment agent composed of rutile-type titanium and rutile-type titanium and comprising SiO ₂ , Al ₂ O ₃ , and polyol, the white pigment has a hydrophilic effect due to the hydrophilic group imparting effect. Since the SiO ₂ surface treatment agent adheres firmly to the rutile type titanium and the SiO ₂ layer blocks the oil and fat content of the contents in the retort packaging bag made of this laminated film for packaging, photooxidation of the rutile type titanium Due to the reaction, there is an effect that the deterioration of the oil and fat in contact with the rutile type titanium occurs and the occurrence of abnormal odor is prevented.
Further, in a packaging laminated film having a white colored layer and a gray light-shielding layer, the gray light-shielding layer prevents the transmission of sunlight or fluorescence, the contents are decomposed or altered, or a fading or other light deterioration occurs. To prevent. Furthermore, in packaging laminated films having a white colored layer and a black light-shielding layer, the black light-shielding layer completely blocks the transmission of sunlight, fluorescence, etc., the contents are decomposed or altered, or the occurrence of fading or other light deterioration occurs. To prevent.
The laminated film for packaging having this black light-shielding layer has extremely excellent utility as a packaging material for photosensitive materials as industrial members that require complete light-shielding.
Moreover, the laminated film for packaging of the present invention does not generate harmful substances when incinerated and discarded after use, and is extremely excellent in suitability for disposal and environmental suitability.
In addition, the packaging bag made of the laminated film for packaging of the present invention, especially the retort packaging bag, does not change the odor of the contents even after retort sterilization treatment, and can sufficiently withstand long-term storage. It is.

  The present invention will be described in more detail with reference to the drawings.

  FIG. 1 shows a first embodiment of a laminated film for packaging according to the present invention. FIG. 2 shows a second embodiment of the laminated film for packaging of the present invention. FIG. 3 shows a third embodiment of the laminated film for packaging of the present invention. FIG. 4 shows the fourth embodiment of the laminated film for packaging of the present invention. FIG. 5 shows a fourth embodiment of the laminated film for packaging of the present invention.

As shown in FIG. 1, the laminated film for packaging according to the first embodiment of the present invention comprises a base film 1 and a multilayer unstretched olefin sealant 2A.
The multilayer non-stretched olefin sealant 2A includes a first transparent or translucent resin layer 3a, a white colored layer 4, and a second transparent or translucent resin layer 3b.
The first transparent or translucent resin layer 3a and the second transparent or translucent resin layer 3b are made of polyolefin.
The white colored layer 4 is formed by kneading and molding a polyolefin, a white pigment, a pigment dispersant, and a dispersant.
In this case, the white pigment contains rutile type titanium and a surface treatment agent made of SiO ₂ , Al ₂ O ₃ , and polyol that covers the surface of the rutile type titanium.

The SiO ₂ contained in the white pigment adheres firmly to the rutile type titanium, blocks the oil and fat content of the contents in the packaging bag, and deteriorates the fat and oil contacted with the rutile type titanium by the photooxidation reaction of the rutile type titanium. Is prevented from occurring.
Al ₂ O ₃ is used as a treating agent for improving pigment color and anti-chalk properties.
The polyol is used as a treating agent for improving the dispersibility of rutile titanium.
As the polyol, for example, mannitol, sorbitol, fructose, dextrose, reprose, pentaerythritol, anhydroeneneaheptol, and invert sugar (α-D-glucopyranose + β-D-fructofuranose, 1: 1 molar ratio) are applied. Can do.
The white pigment is prepared by dissolving a polyol in a suitable solvent, such as water, and adding a solution of this polyol into a rutile titanium slurry containing SiO ₂ and Al ₂ O ₃ , and then SiO ₂ , Al _2. The slurry can be stirred and dried until O ₃ and polyol are uniformly dispersed.

Rutile titanium ratio of SiO _2, Al ₂ O ₃ and polyols, rutile titanium _{(purity): 90~95wt%, SiO 2:} 3.5~5.0wt%, Al 2 O 3: 2.0 It is preferable that it is -3.5 wt% and polyol: 0-1.0 wt%.

  As the dispersant, for example, magnesium stearate can be used. The addition rate is 0.001% or more and 1.0%, and it is desirable that the dispersant is not added as much as possible.

  The transparent to translucent resin layers 3a and 3b basically function as a protective layer for protecting the white colored layer 4a, and in some cases, on the transparent to translucent resin layers 3a and 3b, for example, When a desired character, symbol, pattern, figure or other printed pattern is formed directly or indirectly, the transparent or translucent resin layer acts as a base layer for making the printed pattern clear and transparent or translucent. The resin layers 3a and 3b act as a heat-sealable resin layer that constitutes the seal portion.

  On the back surface of the base film 1, for example, a desired character, symbol, pattern, figure, or other printed pattern (not shown) is formed, and then a multilayer unstretched olefin sealant 2A is applied to the base film 1 by, for example, dry lamination The laminated film for packaging of the present invention can be produced by laminating by a method such as the above.

In the laminated film for packaging according to the first embodiment of the present invention, the multilayer unstretched olefin sealant 2 is a light-shielding material and also acts as a heat-sealable resin layer. In addition, it has excellent laminate strength, heat seal strength, etc., has further strength, and is excellent in weather resistance, heat resistance, water resistance and other fastness properties, particularly excellent in light shielding properties, sunlight or fluorescent Blocks transmission, acts as a light shield to prevent decomposition, alteration, browning and other light deterioration of the package contents. In addition, SiO ₂ contained in the white pigment adheres firmly to rutile titanium and is contained in the packaging bag. Oils and fats in the contents are cut off, and the photo-oxidation reaction of rutile titanium prevents the fats and oils in contact with the rutile titanium from deteriorating, and generates hazardous substances when incinerated and discarded after use. Rukoto has the advantage that there is no, and does not react to the metal (foreign matter) detector.

  As shown in FIG. 2, the laminated film for packaging according to the second embodiment of the present invention includes a base film 1 and a multilayer unstretched olefin sealant 2B. The multi-layer non-stretched olefin sealant 2B includes a first transparent or translucent resin layer 3a, a white colored layer 4, a gray layer adjacent to the white colored layer 4 and laminated on the opposite side of the base film 1. It consists of a light shielding layer 5 and a second transparent or translucent resin layer 3b. The first transparent or translucent resin layer 3a and the second transparent or translucent resin layer 3b are made of polyolefin, and this is as described in the description of the first embodiment. The white colored layer 4 has the same configuration as the white colored layer 4 in the first embodiment.

The gray light shielding layer 5 is formed by kneading and molding polyolefin, a white pigment, a black pigment, and a dispersant.
The white pigment is composed of rutile titanium and a surface treatment agent composed of SiO ₂ , Al ₂ O ₃ and a polyol which covers the surface of the rutile titanium particles.
Rutile titanium ratio of SiO _2, Al ₂ O ₃ and polyols, rutile titanium _{(purity): 90~95wt%, SiO 2:} 3.5~5.0wt%, Al 2 O 3: 2.0 It is preferable that it is -3.5 wt% and polyol: 0-1.0 wt%.
In this embodiment, the content of the white pigment is 5 to 30 times that of the black pigment.
Further, iron black, graphite, or carbon black can be used as the black pigment, and benzpyrene-free carbon black having a benzpyrene concentration of 5 ppb or less that avoids the incorporation of benzpyrene, which has been pointed out as carcinogenic in recent years, is particularly preferable.
As the dispersant, for example, magnesium stearate can be used. The addition rate is 0.001% or more and 1.0%, and it is desirable that the dispersant is not added as much as possible.

The gray light-shielding layer 5 prevents sunlight or fluorescence from being transmitted, and the contents are decomposed or altered, or the occurrence of fading or other light deterioration is prevented.
Similarly to the case of the white colored layer 4, the white pigment contained in the gray light-shielding layer 5 is composed of rutile titanium, rutile titanium, and SiO ₂ , Al ₂ O ₃ and polyol covering the surface of rutile titanium. Since the surface treatment agent is included, the SiO ₂ surface treatment agent having a hydrophilic effect due to the hydrophilic group imparting effect adheres firmly to the rutile titanium, and the contents in the packaging bag constituted by the laminated film for packaging of SiO ₂ Since the oil and fat content of the rutile type titanium is blocked, the photo-oxidation reaction of the rutile type titanium prevents the fat and oil in contact with the rutile type titanium from being deteriorated, thereby preventing the occurrence of abnormal odor.
Further, as the black pigment, iron black, graphite or carbon black can be used as the black pigment. In particular, a benzpyrene-free carbon black having a benzpyrene concentration of 5 ppb or less that avoids mixing of benzpyrene, which has been pointed out as carcinogenic in recent years, is available. preferable.

In the laminated film for packaging according to the second embodiment of the present invention, the multilayer unstretched olefin sealant 2 is a light-shielding material and also acts as a heat-sealable resin layer, and has excellent light-shielding properties or light-shielding properties, and It is an aluminum-less material, and also has excellent laminate strength, heat seal strength, etc., and further strength, weather resistance, heat resistance, water resistance and other fastness properties, particularly excellent light shielding properties, Blocks light or fluorescence transmission, acts as a light shield to prevent decomposition, alteration, browning and other light degradation of the package contents. In addition, SiO ₂ contained in the white pigment adheres firmly to rutile titanium. , Block the oil and fat content in the packaging bag, prevent the rutile titanium photooxidation reaction from deteriorating the oil and fat in contact with the rutile titanium, and when incineration disposal after use It has the advantage that without generating substances, and does not react to the metal (foreign matter) detector.

  As shown in FIG. 3, the laminated film for packaging according to the third embodiment of the present invention comprises a base film 1 and a multilayer unstretched olefin sealant 2C. The multilayer non-stretched olefin sealant 2C is adjacent to the first transparent or translucent resin layer 3a, the first white colored layer 4a, and the first white colored layer 4a, and is located on the opposite side to the base film 1. The gray light-shielding layer 5, the second white colored layer 4b, and the second transparent or translucent resin layer 3b are stacked. The first transparent or translucent resin layer 3a and the second transparent or translucent bright resin layer 3b are made of polyolefin, and this is as described in the description of the first embodiment. The first white colored layer 4a and the second white colored layer 4b have the same configuration as the white colored layer 4 in the first embodiment. Further, the gray light shielding layer 5 has the same configuration as the gray light shielding layer 5 in the second embodiment.

  In this embodiment, since the second white colored layer 5b is laminated, the transmission of sunlight or fluorescence is prevented, the contents are decomposed or altered, or the occurrence of fading or other light deterioration is prevented. The effect is further enhanced.

In the laminated film for packaging according to the third embodiment of the present invention, the multilayer unstretched olefin sealant 2 is a light-shielding material and also functions as a heat-sealable resin layer. It is an aluminum-less material, and also has excellent laminate strength, heat seal strength, etc., and further strength, weather resistance, heat resistance, water resistance and other fastness properties, particularly excellent light shielding properties, Blocks light or fluorescence transmission, acts as a light shield to prevent decomposition, alteration, browning and other light degradation of the package contents. In addition, SiO ₂ contained in the white pigment adheres firmly to rutile titanium. , Block the oil and fat content in the packaging bag, prevent the rutile titanium photooxidation reaction from deteriorating the oil and fat in contact with the rutile titanium, and when incineration disposal after use It has the advantage that without generating substances, and does not react to the metal (foreign matter) detector.

  As shown in FIG. 4, the laminated film for packaging according to the fourth embodiment of the present invention includes a base film 1 and a multilayer unstretched olefin sealant 2D. The multi-layer non-stretched olefin sealant 2D is a black layer that is laminated adjacent to the first transparent or translucent resin layer 3a, the white colored layer 4, the white colored layer 4 and on the opposite side of the base film 1. It consists of a light shielding layer 6 and a second transparent or translucent resin layer 3b. The first transparent or translucent resin layer 3a and the second transparent or translucent resin layer 3b are made of polyolefin, and this is as described in the description of the first embodiment. The white colored layer 4 has the same configuration as the white colored layer 4 in the first embodiment.

  The black light shielding layer 6 is formed by kneading and molding polyolefin, a black pigment, and a dispersant. Although iron black, graphite, or carbon black can be used, benzpyrene-free carbon black having a benzpyrene concentration of 5 ppb or less that avoids mixing of benzpyrene, which has been pointed out as carcinogenic in recent years, is particularly preferable. The amount of the black pigment used is preferably about 0.1% to 5.0% by weight, preferably about 1.0% to 3.0% by weight, based on the polyolefin.

  In this embodiment, since the black light-shielding layer 6 is laminated, there is an effect of preventing the transmission of sunlight, fluorescence, etc., decomposing or altering the contents, or preventing the occurrence of fading or other light deterioration. It is further enhanced.

In the laminated film for packaging of the fourth embodiment of the present invention, the multilayer unstretched olefin sealant 2 is a light-shielding material and also acts as a heat-sealable resin layer, and has excellent light-shielding properties or light-shielding properties, and It is an aluminum-less material, and also has excellent laminate strength, heat seal strength, etc., and further strength, weather resistance, heat resistance, water resistance and other fastness properties, particularly excellent light shielding properties, Blocks light or fluorescence transmission, acts as a light shield to prevent decomposition, alteration, browning and other light degradation of the package contents. In addition, SiO ₂ contained in the white pigment adheres firmly to rutile titanium. , Block the oil and fat content in the packaging bag, prevent the rutile titanium photooxidation reaction from deteriorating the oil and fat in contact with the rutile titanium, and when incineration disposal after use It has the advantage that without generating substances, and does not react to the metal (foreign matter) detector.

  As shown in FIG. 5, the laminated film for packaging according to the fifth embodiment of the present invention includes a base film 1 and a multilayer unstretched olefin sealant 2E. The multilayer unstretched olefin sealant 2E is adjacent to the first transparent or translucent resin layer 3a, the first white colored layer 4a, and the first white colored layer 4a, and on the opposite side of the base film 1 The black light shielding layer 6 laminated in this manner, the second white colored layer 4b laminated adjacent to the black light shielding layer 6, and the second transparent resin layer 3b. The first transparent or translucent resin layer 3a and the second transparent or translucent resin layer 3b are made of polyolefin, and this is as described in the description of the first embodiment. The first white colored layer 4a and the second white colored layer 4b have the same configuration as the white colored layer 4 in the first embodiment. The black light shielding layer 6 has the same configuration as the black light shielding layer 6 in the fourth embodiment.

  In this embodiment, since the black light-shielding layer 6 and the second white colored layer 4b are laminated, the transmission of sunlight or fluorescence is prevented, the contents are decomposed or altered, or the light is amber or other light. The effect of preventing the occurrence of deterioration is further enhanced.

In the laminated film for packaging according to the fifth embodiment of the present invention, the multilayer unstretched olefin sealant 2 is a light-shielding material and also acts as a heat-sealable resin layer, and has excellent light-shielding properties or light-shielding properties, and It is an aluminum-less material, and also has excellent laminate strength, heat seal strength, etc., and further strength, weather resistance, heat resistance, water resistance and other fastness properties, particularly excellent light shielding properties, Blocks light or fluorescence transmission, acts as a light shield to prevent decomposition, alteration, browning and other light degradation of the package contents. In addition, SiO ₂ contained in the white pigment adheres firmly to rutile titanium. , Block the oil and fat content in the packaging bag, prevent the rutile titanium photooxidation reaction from deteriorating the oil and fat in contact with the rutile titanium, and when incineration disposal after use It has the advantage that without generating substances, and does not react to the metal (foreign matter) detector.

The polyolefin constituting each layer in the first to fifth embodiments is polypropylene, propylene-ethylenepropylene rubber block copolymer, propylene-ethylene random copolymer, high-pressure method low-density polyethylene, ethylene-α-olefin copolymer. , Medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, and a combination of any two or more of the above olefins can be used.
Therefore, in the present invention, it is preferable to use a polypropylene-based resin having excellent melt tension and stretchability and suitable for inflation as the polyolefin. Specifically, long chain branching is introduced into the main chain of the polypropylene resin. Thus, it is preferable to use a material in which the tension in the molten state is increased.
In the present invention, specifically, as a polypropylene resin excellent in melt tension and stretchability, it is desirable to use a polypropylene resin composed of a block or random copolymer of propylene and ethylene or propylene and 1-octene. .

Thus, in a polypropylene resin comprising a block or random copolymer of propylene and ethylene or propylene and 1-octene, the density is about 0.9 [g / 10 min], and the melt flow rate ( MFR) is in the range of 0.1 to 2.0 [g / 10 min], and melt tension is in the range of 100 [mN] or more (10 [cN] or more). .
Thus, when the MFR is less than 0.1 [g / 10 min], the resin pressure increases during resin extrusion, which is not preferable because of a large load on the film forming machine, Those exceeding 2.0 [g / 10 min] are not suitable for the method of forming the top blown inflation film and are not preferable because they do not blow upward.
For the above polyolefin, if necessary, for example, the main component of the vehicle is film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, difficulty. In order to improve flame retardancy, weather resistance, electrical properties, strength, etc., one or more kinds of various plastic compounding agents and additives are optionally added, and if necessary, solvents and diluents Etc. can be added and sufficiently kneaded to prepare a resin composition constituting each layer in the first to fifth embodiments.

  In the present invention, in the resin composition constituting each layer of the multilayer unstretched olefin sealant, as a plastic compounding agent or additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcement Agents, antistatic agents, flame retardants, flame retardants, foaming agents, antifungal agents, pigments, dyes, dispersants, surfactants, antiblocking agents, etc., and resins for modifiers, etc. Further, the amount of addition can be arbitrarily adjusted from a very small amount to several tens of weight% according to the purpose.

In addition, as the plastic compounding agent and additive, specifically, a lubricant having its own lubricity and little migration in the resin can be used. For example, liquid paraffin, white petrolatum, petroleum wax , Waxes such as microcrystalline wax, montan wax, polyethylene wax, higher fatty acids having 8 to 22 carbon atoms, or higher fatty acids such as higher fatty acid aluminum, higher fatty acid calcium, higher fatty acid magnesium, higher fatty acid zinc, higher fatty acid lithium, etc. Or metal salts thereof, linear aliphatic monohydric alcohols having 8 to 18 carbon atoms, fatty acid alcohols such as glycerin, sorbitol, propylene glycol, pentaerythritol and triethylene glycol, higher fatty acids and carbon having 4 to 22 carbon atoms 8-18 straight-chain aliphatic monovalent al Esters, triacetyl citrate, di-2-ethyl-hexyl adipate, azelaic acid-n-hexyl, ethanediol montanate, poly (1,3-butanediol adipic acid) ester, acetylricinoleic acid Esters of alcohols and fatty acids such as methyl, poly (1,3-butylene glycol, 1,4-butylene glycol, octyl alcohol adipate) ester, hydrogenated edible oils, sesame oil, spalm acetyl wax, acetylated monoglyceride Glycerides such as ethylene bis fatty acid amide represented by ethylene bis oleyl amide having 16 to 18 carbon atoms, higher fatty acid amide having 8 to 22 carbon atoms, stearyl erucamide, erucic acid amide, oleyl palmitoamide, etc. Higher fatty acid amides In addition, use one or more of silicone oils such as methylhydrodiene polysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, polyoxyalkylene dimethylsiloxane, and glycerin ester of rosin and maleic acid modified rosin. Can do.
In the present invention, among the above-mentioned lubricants, erucic acid amide, ethylene bisoleyl amide, stearic acid amide, oleic acid amide, methylene bis stearic acid amide, etc. themselves have lubricity and are extremely effective. Material.
The addition amount of the lubricant is preferably 0.08 to 10.0 parts by weight with respect to 100 parts by weight of polyolefin.

In the present invention, other oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide and zinc oxide, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, and carbonate Anti-blocking of carbonates such as magnesium and calcium carbonate, sulfates such as calcium sulfate and barium sulfate, silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate, and other inorganic compounds such as kaolin, talc and diatomaceous earth Anti-blocking of organic compounds consisting of agents, high-density polyethylene, ultra-high molecular weight polyethylene with a molecular weight of 300,000 or more, polypropylene, polycarbonate, polyamide, polyester, melamine resin, diallyl phthalate resin, acrylic resin and other fine powders One or two or more of may be added to the resin composition.
The amount added is preferably about 0.01 to 3 parts by weight per 100 parts by weight of polyolefin.

  Next, a method for producing a multilayer unstretched olefin sealant in the present invention will be described. First, the core resin composition as described above is prepared, and then the resin composition is co-extruded using, for example, a T-die co-extruder, an inflation co-extruder or the like to obtain a multilayer unstretched olefin sealant. obtain.

Next, the film thickness of the multilayer unstretched olefin sealant is preferably about 15 μm to 180 μm, preferably about 30 μm to 150 μm.
Thus, as the film thickness of each layer constituting the multilayer unstretched olefin sealant according to the present invention, the film thickness of the gray light shielding layer or the black light shielding layer is 3 μm to 30 μm, preferably 5 μm to 30 μm, preferably 5 μm to 20 μm, white colored layer having a thickness of 5 μm to 30 μm, preferably 10 μm to 20 μm, and transparent to translucent resin layer having a thickness of 5 μm to 100 μm, preferably in the range of 10 μm to 80 μm. It is preferable.
If the thickness of the gray light-shielding layer or the black light-shielding layer is less than 3 μm, the function as the gray light-shielding layer or the black light-shielding layer is lowered, and there is a possibility that the thickness may be greatly affected by the uneven thickness. On the other hand, when the thickness exceeds 30 μm, it is difficult to set a white colored layer for concealing it.
If the thickness of the white colored layer is less than 5 μm, it is difficult to conceal the gray light-shielding layer or the black light-shielding layer, and the function as a heat-sealable resin is further reduced, which is not preferable. On the other hand, if the thickness exceeds 30 μm, the entire film thickness increases, and the influence on the environment as packaging waste increases, which is not preferable.
If the film thickness of the transparent or translucent resin layer is less than 5 μm, the protective properties of the package contents are lowered, the appearance and aesthetics are lowered, and further the function as a heat sealable resin is also lowered. It is not preferable. On the other hand, when the film thickness exceeds 100 μm, the entire film thickness increases, which is not preferable in terms of environmental friendliness when discarded.

The multilayer unstretched olefin sealant in the present invention is a light-shielding material and also acts as a heat-sealable resin layer, is excellent in light-shielding properties, has strength, and has weather resistance, heat resistance, water resistance and other fastness properties. Excellent in light-blocking property or light-blocking property, for example, blocking the transmission of the sun or fluorescence, etc., preventing the content from being decomposed or altered, or preventing brown or other light deterioration, suitability for filling and packaging the content It has excellent storage properties and is extremely useful as a packaging material for photosensitive materials as well as foods. Furthermore, there are advantages that no harmful substances are generated when incinerated and discarded after the packaging material is used, and that a metal piece (foreign material) can be easily detected by a metal detector.
Furthermore, since the white pigment of the white colored layer and the gray light-shielding layer contains a surface treatment agent comprising SiO ₂ , Al ₂ O ₃ and a polyol which covers the surface of rutile titanium and rutile titanium, a hydrophilic group The SiO ₂ surface treatment agent that has a hydrophilic effect due to the imparting effect adheres firmly to the rutile titanium, and the SiO ₂ layer blocks the oil and fat content of the contents in the retort packaging bag made of this laminated film for packaging. The SiO ₂ surface treatment agent having a hydrophilic effect due to the hydrophilic group imparting effect adheres firmly to the rutile type titanium, and the SiO ₂ layer reduces the fat and oil content of the contents in the retort packaging bag made of this laminated film for packaging. Since it is blocked, the photooxidation reaction of the rutile type titanium brings about a characteristic effect of the present invention that the fat and oil contacted with the rutile type titanium is deteriorated and the occurrence of abnormal odor is prevented.

The base film 1 is excellent in mechanical, physical, chemical and other properties, excellent in strength, toughness, etc., and further excellent in heat resistance, moisture resistance, pinhole resistance, puncture resistance, transparency, and the like. A resin film or sheet can be used.
Specifically, unstretched or uniaxial or biaxially stretched films of resins such as polyester resins, polyamide resins, polyaramid resins, polyethylene resins, polypropylene resins, polycarbonate resins, polyacetal resins, fluorine resins, etc. Or a sheet can be used.
The thickness of the resin film or sheet described above may be a thickness that can maintain strength, puncture resistance, rigidity, and the like to the minimum necessary.
For the reasons described above, the thickness of the resin film described above is most desirably about 10 μm to 100 μm, preferably about 12 μm to 50 μm.
Among the above-described resin films or sheets, in particular, a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, a biaxially stretched polypropylene resin film, and a biaxially stretched polyester resin film having a thickness of about 9 μm to 30 μm. It is desirable to use a laminated film of the biaxially stretched polyamide resin film.

As the other base film 1, a material having a property of shielding sunlight or a property of not transmitting gas such as water vapor, water, oxygen, or the like can be used.
Specifically, for example, a resin film having a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide having a barrier property, low density polyethylene having a barrier property such as water vapor or water, medium density polyethylene, high density polyethylene, Resin film or sheet such as linear low density polyethylene, polypropylene, ethylene-propylene copolymer, etc., polyvinyl alcohol having gas barrier properties, saponified ethylene-vinyl acetate copolymer, nylon MXD6 resin film or sheet, Various colored resin films or sheets having light-shielding properties, which are formed by adding a colorant such as a pigment and other desired additives to the resin and kneading them into a film, can be used.
These materials can be used alone or in combination.
The thickness of the film or sheet is usually about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

Furthermore, as the deposited film of the inorganic oxide, a film having a thickness of about 100 to 2000 mm can be used.
Examples of the film or sheet for supporting the vapor-deposited film of inorganic oxide include, for example, polyester film, polyamide film, polyolefin film, polyvinyl chloride film, polycarbonate film, polyvinylidene chloride film, polyvinyl alcohol film, and ethylene-vinyl acetate. Polymer saponified products and the like can be used.

As the inorganic oxide constituting the vapor-deposited film of inorganic oxide, for example, silicon oxide, aluminum oxide, indium oxide, tin oxide, zirconium oxide and the like can be used.
Furthermore, a mixture of silicon monoxide and silicon dioxide or a mixture of silicon oxide and aluminum oxide can be used as the inorganic oxide.
The inorganic oxide vapor deposition film can be formed by a vacuum vapor deposition method such as an ion beam method or an electron beam method, a sputtering method, or the like.
In order to obtain a sufficient barrier property, the thickness of the inorganic oxide vapor-deposited film is usually preferably about 100 to 2000 mm, and more preferably about 200 to 1500 mm.
If the thickness of the inorganic oxide vapor deposition film exceeds 1500 mm, particularly if it exceeds 2000 mm, there is a risk that the inorganic oxide vapor deposition film is liable to crack and the like, thereby reducing the barrier properties and the material. This is not preferable because the cost increases. On the other hand, when it is less than 100 mm, particularly less than 200 mm, it is difficult to recognize the barrier effect, which is not preferable.

Next, in the present invention, as the base film 1, a resin that has a low adsorption of perfume ingredients and the like contained in the contents to be packaged, is rich in aroma retention, and does not cause a change in taste, off-flavor, etc. The film or sheet can be used.
Specifically, for example, polyacrylic resins, polymethacrylic resins, polyacrylotolyl resins, polymethacrylonitrile resins, polystyrene resins, polycarbonate resins, polyethylene terephthalate resins or their ethylene components and / or terephthalates. A part of the components are copolymerized or modified with other dialcohols or higher polyhydric alcohol components or dicarboxylic acid components, polyester resins such as polyethylene naphthalate resins, polyamide resins, ethylene-vinyl acetate copolymer. Polymer saponified products, polyvinyl alcohol resins, polyvinyl chloride resins, polyvinylidene chloride resins, and other resin films or sheets can be used.
Therefore, in the present invention, among the above resin films or sheets, it is desirable to use a resin film or sheet having a fragrance retention property and a barrier property against oxygen gas or water vapor. For example, it is desirable to use a resin film or sheet made of a saponified product of an ethylene-vinyl acetate copolymer, a polyamide resin, a polyacrylo resin, or a polyester resin and having a high aroma retaining property and a barrier property.

  Furthermore, in the present invention, as the base film 1, in addition to the above-mentioned base film, for example, in order to impart formability, bending resistance, rigidity, etc., for example, a strongly sized bleached or unbleached paper base is used. Materials or paper base materials such as pure white roll paper, kraft paper, paperboard, and processed paper can be laminated.

In the present invention, an arbitrary printed pattern layer can be provided on the front surface or the back surface of any layer constituting the packaging laminated film.
Specifically, the printed pattern layer is mainly composed of an ink vehicle composed of one or more kinds of resins and the like, and if necessary, a plasticizer, a stabilizer, an antioxidant, and a light stabilizer. 1 to 2 or more kinds of additives, UV absorbers, curing agents, cross-linking agents, lubricants, antistatic agents, fillers and other additives are optionally added, and colorants such as dyes and pigments are added, and solvents are added. The ink composition is prepared by sufficiently kneading with a diluent, etc., and then using this ink composition, for example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing and other printing methods Thus, for example, a printed pattern layer can be provided on the base film 1.

  In the present invention, as a method of bonding the base film 1 and the multilayer unstretched olefin sealant layers 2A to 2E, for example, the base film 1 and the multilayer unstretched olefin sealant layers 2A to 2E are laminated via an adhesive layer for laminating. Or a melt extrusion lamination method in which the base film 1 and the multilayer unstretched olefin sealant layer 2 are laminated via an anchor coating agent layer and a melt extrusion resin layer.

In the present invention, examples of the laminating adhesive used when the base film 1 is bonded to the multilayer unstretched olefin sealants 2A to 2E include, for example, a polyvinyl acetate adhesive, acrylic acid ethyl, butyl, and 2-ethylhexyl ester. Homopolymers such as these, or polyacrylic acid ester adhesives composed of copolymers of these with methyl methacrylate, acrylonitrile, styrene, etc., cyanoacrylate adhesives, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, Copolymer adhesives with monomers such as methacrylic acid, cellulose adhesives, polyester light adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenol resin Adhesive, epoxy adhesive, polyurethane adhesive Agent, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, rubber adhesive made of styrene-butadiene rubber, silicone adhesive, alkali metal silicate, inorganic adhesive made of low melting glass, etc. The adhesive can be used.
The composition system of the above-mentioned adhesive may be in any form of composition such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the properties thereof are film or sheet, powder, solid, etc. Any form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
Thus, the adhesive is applied to the surface of the base film 1 or the multilayer unstretched olefin sealant 2 to be bonded thereto by, for example, a roll coating method, a gravure roll coating method, a kiss coating method or other coating methods, or a printing method. The coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Next, the anchor coating agent used when the base film 1 is bonded to the multilayer unstretched olefin sealant 2 will be described. Examples of the anchor coating agent that can be used include organic titanium-based, isocyanate-based, polyethyleneimine-based, polybutadiene-based, and other water-based or oil-based anchor coating agents such as alkyl titanates.
The anchor coating agent can be coated by, for example, roll coating, gravure roll coating, kiss coating, or other coating methods. The coating amount is preferably about 0.1 to 5 g / m ² (dry state).

Examples of the melt-extruded resin layer in the above-described extrusion lamination method include polyethylene resins, polypropylene resins, acid-modified polyethylene resins, acid-modified polypropylene resins, ethylene-acrylic acid or methacrylic acid copolymers, and Surlyn. 1 type or 2 or more types of thermoplastic resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic acid ester copolymer, polystyrene resin, polyvinyl chloride resin and other thermoplastic resins Can be used.
In the above extrusion lamination method, in order to obtain stronger adhesive strength, for example, lamination can be performed via an anchor coating agent.

As the primer layer, for example, polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene or polypropylene, The primer agent layer can be formed using a resin composition containing the copolymer or modified resin, cellulose resin or the like as a main component of the vehicle.
In the present invention, the primer layer can be formed using, for example, roll coating, gravure coating, kiss coating or other coating methods. Thus, the coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Using the laminated film for packaging according to the first to fifth embodiments, the center seal portion 9 and the lower seal portion 10a are sealed as shown in FIG. A retort packaging bag in the form of a sealed pillow packaging bag can be produced. Further, the form of the packaging bag is not limited to that shown in FIG. 6, and may be any form of a two-side sealed packaging bag, a three-side sealed packaging bag, a four-side sealed bag, a standing pouch, and a square bottom bag. .
The retort packaging bag made of the laminated film for packaging according to the present invention does not change the odor of the contents even if the retort treatment is performed, and can sufficiently withstand long-term storage.
In addition to a packaging bag, a laminated material in which a paper base material is laminated is produced as a laminated film for packaging, and a blank plate is produced using this laminated material. A paper container can be manufactured.

The packaging bag using the laminated film for packaging of the present invention is, for example, food and drink, fruit juice, drinking water, liquor, cooked food, marine product, frozen food, meat product, boiled food, rice cake, liquid soup, seasoning and other Various foods and drinks can be filled and packaged.
Thus, in the present invention, for example, a standing pouch for filling and packaging soy sauce, sauce, soup, etc., a standing pouch for filling and packaging fresh confectionery, a standing pouch for filling and packaging frozen food, or a retort food packaging It is useful as a standing pouch such as a standing pouch for filling and packaging liquid food and drink such as a standing pouch or food and drink containing moisture.
Next, the present invention will be described more specifically with reference to examples.

(1) First, the following resin compositions (a), (b), (c) and (d) were prepared.
(A) Resin composition constituting the first layer Functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) and 10.0 parts by weight A resin composition constituting the first layer was prepared.
(B) Resin composition constituting the second layer 79.7 parts by weight of a functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) rutile titanium _{purity: 2.6%, SiO 2::} 93%, Al 2 O 3 as a surface treatment agent 4.1%, polyol: titanium oxide pigment 20.0 parts by weight of the composition consisting of 0.3% A resin composition constituting the second layer was prepared by sufficiently kneading 0.3 parts by weight of Mg stearate as a pigment dispersant.
(C) Resin composition constituting the third layer 73.1 parts by weight of a functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min), Rutile-type titanium content: 93%, Al ₂ O ₃ as a surface treatment agent: 2.6%, SiO ₂ : 4.1%, polyol: 0.3% titanium oxide pigment 25.0 parts by weight Then, 1.1 parts by weight of benzpyrene-free carbon black as a black pigment and 0.4 parts by weight of Mg stearate as a pigment dispersant were sufficiently kneaded to prepare a resin composition constituting the third layer.
(D) Resin composition constituting the fourth layer Functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) and 100.0 parts by weight were synthesized. A resin composition constituting the fourth layer was prepared by sufficiently kneading 0.5 part by weight of silica, 0.05 part by weight of erucic acid amide, and 0.05 part by weight of ethylene bisoleic acid amide.

(2) (4) Resin composition layer 10 μm, (b) Resin composition layer 20 μm, (C) Resin composition layer 10 μm, (4) A multi-layer unstretched olefin sealant having a total thickness of 70 μm composed of four resin composition layers of 30 μm was manufactured.
(3) Corona treatment is applied to the surface of the first layer of the multilayer non-stretched sealant, and a two-component curable urethane adhesive (main agent: polyester polyol, hardener: aliphatic isocyanate) is applied to the surface, and a stretched polyamide film (Unitika Emblem ONBC) 15 [mu] m was bonded, and then stretched polyester-based silica vapor deposited film (IB-PET-RB) 12 [mu] m was similarly bonded to the stretched polyamide-based film through a two-component urethane adhesive. A laminated film for packaging was produced.
(4) A four-sided pouch having a size of 130 mm × 170 mm was prepared from the produced laminated film for packaging using an impulse sealer, and was prepared from 15 g of butter, 15 g of flour, 200 ml of milk, salt and pepper in this pouch. 200 g of white sauce was filled and the mouth of the pouch was sealed. The sealed retort packaging bag was subjected to a retort sterilization treatment at 120 ° C. for 30 minutes to prepare a white sauce packaging bag for storage.
After a retort sterilization treatment, a storage test was conducted for 1 month in a light irradiation environment at 37 ° C. and 1600 lux. As a result, the discoloration and odor of the package contents were not observed.

(1) First, the following resin compositions (a), (b), (c), (d) and (e) were prepared.
(I) Resin composition constituting the first layer Functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) 100.0 parts by weight A resin composition constituting the first layer was prepared.
(B) Resin composition constituting the second layer 79.7 parts by weight of a functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) Rutile-type titanium content: 93%, titanium oxide pigment having a composition comprising Al ₂ O ₃ as a surface treatment agent: 2.5%, SiO ₂ : 4.0%, polyol: 0.5% 20.0 parts by weight A resin composition constituting the second layer was prepared by sufficiently kneading 0.3 parts by weight of Mg stearate as a pigment dispersant.
(C) Resin composition constituting the third layer 73.1 parts by weight of a functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min), Rutile titanium pure content: 93%, Al ₂ O ₃ as a surface treatment agent: 2.5%, SiO ₂ : 4.1%, polyol: 0.3% titanium oxide pigment 25.0 parts by weight Then, 1.1 parts by weight of benzpyrene-free carbon black as a black pigment and 0.4 parts by weight of Mg stearate as a pigment dispersant were sufficiently kneaded to prepare a resin composition constituting the third layer.
(D) Resin composition constituting the fourth layer Functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min), 79.7 parts by weight, Rutile-type titanium content: 93%, titanium oxide pigment having a composition comprising Al ₂ O ₃ as a surface treatment agent: 2.5%, SiO ₂ : 4.0%, polyol: 0.5% 20.0 parts by weight A resin composition constituting the fourth layer was prepared by sufficiently kneading 0.3 parts by weight of Mg stearate as a pigment dispersant.
(E) Resin composition constituting the fifth layer 100.0 parts by weight of a functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) Synthetic silica 0.5 parts by weight, erucic acid amide 0.05 parts by weight, and ethylene bisolefinic acid amide 0.05 parts by weight were sufficiently kneaded to prepare a resin composition constituting the fifth layer.

(2) (5) Resin composition layer 10 μm, (b) Resin composition layer 20 μm, (C) Resin composition layer 10 μm, (5) A multi-layer unstretched olefin sealant having a total thickness of 70 μm consisting of 5 layers of resin composition layer 10 μm and (e) resin composition layer 20 μm was produced.
(3) Corona treatment is applied to the surface of the first layer of the multilayer non-stretched sealant, and a two-component curable urethane adhesive (main agent: polyester polyol, hardener: aliphatic isocyanate) is applied to the surface, and a stretched polyamide film (Unitika Emblem ONBC) 15 [mu] m was bonded, and then stretched polyester-based silica vapor deposited film (IB-PET-RB) 12 [mu] m was similarly bonded to the stretched polyamide-based film through a two-component urethane adhesive. A laminated film for packaging was produced.
(4) A four-sided pouch with a size of 150 mm × 180 mm was prepared from the produced laminated film for packaging using an impulse sealer, and was prepared from 15 g of butter, 15 g of flour, 200 ml of milk, salt and pepper a little in this pouch. 200 g of white sauce was filled and the mouth of the pouch was sealed. The sealed retort packaging bag was subjected to a retort sterilization treatment at 120 ° C. for 30 minutes to prepare a white sauce packaging bag for storage.
After a retort sterilization treatment, a storage test was conducted for 1 month in a light irradiation environment at 37 ° C. and 1600 lux. As a result, the discoloration and odor of the package contents were not observed.

(1) First, the following resin compositions (a), (b), (c) and (d) were prepared.
(A) Resin composition constituting the first layer Ethylene-α-olefin polymer polymerized using a single-site catalyst (metallocene catalyst) (Evolution SP2020 manufactured by Mitsui Chemicals, Inc.): Density = 0.916 g / cm ³ , MFR = 1.5 g / 10 minutes) A resin composition constituting the first layer comprising 100.0 parts by weight was prepared.
(B) Resin composition constituting the second layer Ethylene-α-olefin polymer polymerized using a single-site catalyst (metallocene catalyst) (Evolution SP2020 manufactured by Mitsui Chemicals, Inc.): Density = 0.916 g / cm ³ , MFR = 1.5 g / 10 minutes) 79.7 parts by weight, pure rutile titanium content: 93%, Al ₂ O ₃ as a surface treatment agent: 2.6%, SiO ₂ : 4.1%, Polyol: A resin composition constituting the second layer was prepared by sufficiently kneading 20.0 parts by weight of titanium oxide pigment having a composition of 0.3% and 0.3 parts by weight of Mg stearate as a pigment dispersant.
(C) Resin composition constituting the third layer Ethylene-α-olefin polymer polymerized using a single-site catalyst (metallocene catalyst) (Evolution SP2020 manufactured by Mitsui Chemicals, Inc.): Density = 0.916 g / cm ³ , MFR = 1.5 g / 10 min) 73.1 parts by weight, rutile titanium pure content: 93%, Al ₂ O ₃ as surface treatment agent: 2.5%, SiO ₂ : 4.1%, Polyol: 25.0 parts by weight of a titanium oxide pigment having a composition of 0.5%, 1.5 parts by weight of benzpyrene-free carbon black as a black pigment, and 0.4 parts by weight of Mg stearate as a pigment dispersant are sufficiently kneaded. A resin composition constituting three layers was prepared.
(D) Resin composition constituting the fourth layer Ethylene-α-olefin polymer polymerized using a single-site catalyst (metallocene catalyst) (Evolution SP2020 manufactured by Mitsui Chemicals, Inc.): Density = 0.916 g / cm ³ , MFR = 1.5 g / 10 min) 100.0 parts by weight, synthetic silica 0.5 part by weight, erucic acid amide 0.05 part by weight, ethylenebisoleic acid amide 0.05 part by weight A resin composition constituting the fourth layer was prepared.

(2) (4) Resin composition layer 5 μm, (b) 19 μm resin composition layer, (c) 8 μm resin composition layer, and (d) A multi-layer unstretched olefin sealant having a total thickness of 50 μm consisting of four resin composition layers of 18 μm was produced.
(3) Corona treatment is applied to the surface of the first layer of the multilayer unstretched sealant, and a two-component curable urethane adhesive (main agent: polyester polyol, curing agent: aliphatic isocyanate) is applied to the surface, and polyamide-based silica vapor deposition is applied. A laminated film for packaging was manufactured by laminating 15 μm of a film (IB-ON-FRC manufactured by DNP).
(4) A four-sided pouch with a size of 130 mm x 170 mm is prepared from the produced laminated film for packaging using an impulse sealer, and 100 g of processed fruit (mandarin) is filled in the pouch, and the mouth of the pouch is sealed. did. The sealed retort packaging bag was subjected to boil sterilization at 90 ° C. for 30 minutes to prepare a processed fruit packaging bag for storage.
After performing the boil sterilization treatment, after performing a storage test for one month in a light irradiation environment at 22 ° C. and 1600 lux, opening the packaging bag and observing changes in the processed fruit as the package contents, There was no discoloration or odor deterioration of the package contents.

(1) First, the following resin compositions (a), (b), (c) and (d) were prepared.
(A) Resin composition constituting the first layer 100.0 parts by weight of high-pressure method low-density polyethylene (Novatec LC522 manufactured by Nippon Polyethylene Co., Ltd .: density = 0.923 g / cm ³ , MFR = 4.0 g / 10 min) The resin composition which comprises the 1st layer which consists of was prepared.
(B) Resin composition constituting the second layer High pressure method low density polyethylene (Novatec LC522, manufactured by Nippon Polyethylene Co., Ltd .: density = 0.923 g / cm ³ , MFR = 4.0 g / 10 min) 79.7 parts by weight Titanium oxide pigment 20.0 having a composition comprising: rutile type pure titanium: 93%, Al ₂ O ₃ as a surface treatment agent: 2.6%, SiO ₂ : 4.1%, polyol: 0.3% A resin composition constituting the second layer was prepared by sufficiently kneading 0.3 parts by weight of magnesium stearate as a part by weight and a pigment dispersant.
(C) Resin composition constituting third layer High-pressure method low-density polyethylene (Novatec LC522 manufactured by Nippon Polyethylene Co., Ltd .: density = 0.923 g / cm ³ , MFR = 4.0 g / 10 min) 73.1 parts by weight Titanium oxide pigment 25.0 having a composition comprising: rutile type pure titanium: 93%, Al ₂ O ₃ as a surface treatment agent: 2.6%, SiO ₂ : 4.1%, polyol: 0.3% A resin composition constituting the third layer was prepared by sufficiently kneading 1.5 parts by weight of benzpyrene-free carbon black as a black pigment and 0.4 parts by weight of Mg stearate as a pigment dispersant.
(D) Resin composition constituting the fourth layer High-pressure low-density polyethylene (Novatec LC522 manufactured by Nippon Polyethylene Co., Ltd .: density = 0.923 g / cm ³ , MFR = 4.0 g / 10 min) 100.0 parts by weight And 1.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylenebisoleic acid amide were sufficiently kneaded to prepare a resin composition constituting the fourth layer.

(2) (4) Resin composition layer 5 μm, (b) 19 μm resin composition layer, (c) 8 μm resin composition layer, and (d) A multi-layer unstretched olefin sealant having a total thickness of 50 μm consisting of four resin composition layers of 18 μm was produced.
(3) As shown in a cross-sectional view in FIG. 8, a stretched polyamide film (Emblem ONM manufactured by Toyobo Co., Ltd.) is provided with a printing ink layer 8 on the back surface of a base film 1 having a thickness of 15 μm, and an ethylene-vinyl acetate copolymer. Using a resin (WT-PC agent manufactured by The Inktec Co., Ltd .: melting point 66.8 ° C.), in a pattern as shown in FIG. A softening resin layer 7 was formed. The multilayer unstretched olefin sealant 2 is bonded to the base film 1 using a two-component curable urethane adhesive (main agent: polyester polyol, curing agent: aliphatic isocyanate), and a laminated film for packaging microwave oven cooking products is obtained. Created.
Using this laminated film for packaging, a pillow packaging bag having a size of 130 mm × 240 mm as shown in FIG. 9 was prepared, and a frozen shumai with a tray was prepared in the bag.
And after performing the storage test for 1 month on the light irradiation conditions of -15 degreeC and 1600 lux, the microwave oven heating was performed. During heating in the microwave oven, the high-temperature softening resin layer 7 was softened by the internal pressure that increased with heating, and a high-pressure automatic release function was achieved through the softened high-temperature softening resin layer 7. Moreover, the packaging bag was opened and the change of Shumai, which is the packaged content, was observed. As a result, the discoloration and odor of the package contents were not observed.

(1) First, the following resin compositions (a), (b), (c), (d) and (e) were prepared.
(A) Resin composition constituting the first layer Resin composition constituting the first layer Ethylene-α / olefin polymer (Evole manufactured by Mitsui Chemicals, Inc.) polymerized using a single site catalyst (metallocene catalyst) SP2020: Density = 0.916 g / cm ³ , MFR = 1.5 g / 10 min) A resin composition constituting the first layer consisting of 100.0 parts by weight was prepared.
(B) Resin composition constituting the second layer Ethylene-α-olefin polymer polymerized using a single-site catalyst (metallocene catalyst) (Evolution SP2020 manufactured by Mitsui Chemicals, Inc.): Density = 0.916 g / cm ³ , MFR = 1.5 g / 10 min) 79.7 parts by weight, pure rutile titanium content: 93%, Al ₂ O ₃ as surface treatment agent: 2.5%, SiO ₂ : 4.1%, Polyol: A resin composition constituting the second layer was prepared by sufficiently kneading 20.0 parts by weight of titanium oxide pigment having a composition of 0.3% and 0.3 parts by weight of Mg stearate as a pigment dispersant.
(C) Resin composition constituting the third layer Ethylene-α-olefin polymer polymerized using a single-site catalyst (metallocene catalyst) (Evolution SP2020 manufactured by Mitsui Chemicals, Inc.): Density = 0.916 g / cm ³ , MFR = 1.5 g / 10 min) 73.1 parts by weight, rutile titanium pure content: 93%, Al ₂ O ₃ as surface treatment agent: 2.5%, SiO ₂ : 4.1%, Polyol: 25.0 parts by weight of a titanium oxide pigment having a composition of 0.3%, 1.5 parts by weight of benzpyrene-free carbon black as a black pigment, and 0.4 parts by weight of Mg stearate as a pigment dispersant are sufficiently kneaded. A resin composition constituting three layers was prepared.
(D) Resin composition constituting the fourth layer A fourth composition comprising 100 parts by weight of high-density polyethylene (Hi-Zex 3300F manufactured by Mitsui Chemicals, Inc .: density = 0.950 g / cm ³ , MFR = 1.1 g / 10 min). A resin composition constituting the layer was prepared.
(E) Resin composition constituting the fifth layer 30.0 parts by weight of high-density polyethylene (Hi-Zex 3300F manufactured by Mitsui Chemicals, Inc .: density = 0.950 g / cm ³ , MFR = 1.1 g / 10 min), 70.0 parts by weight of polypropylene (ethylene-propylene random copolymer resin: Novatec FL02C manufactured by Nippon Polypro Co., Ltd., density = 0.9 g / cm ³ , MFR = 18 g / 10 min, tensile modulus = 700 MPa) was sufficiently kneaded. The resin composition constituting the fifth layer was sufficiently kneaded with 0.05 part by weight of the sulphonic acid amide to prepare a resin composition constituting the fifth layer.

(2) (5) Resin composition layer 5 μm, (b) Resin composition layer 19 μm, (C) Resin composition layer 8 μm, (5) A multi-layer unstretched olefin sealant having a total thickness of 50 μm, comprising 5 layers of resin composition layer 13 μm and (e) resin composition layer 5 μm, was produced.
(3) Corona treatment is applied to the surface of the first layer of the multilayer non-stretched sealant, and a two-component curable urethane adhesive (main agent: polyester polyol, hardener: aliphatic isocyanate) is applied to the surface, and stretched polyester silica A laminated film for packaging was manufactured by bonding 12 μm of a vapor-deposited film (IB-PET-RB manufactured by DNP).
(4) Using the produced laminated film for packaging as a lid for a cup-shaped container made of propylene resin, filling the cup-shaped container with “syrup pickled oranges” and placing the lid on the mouth of the cup-shaped container Then, a sealed fruit cup was made by flat sealing under the conditions of a seal temperature of 200 ° C., 1 kg / cm ² for 1 second, and leakage of the package contents and tearing of the lid material were observed for this preserved processed fruit cup. There wasn't. Further, the peel feeling of the cup lid material was good, and no tearing, tearing, stringing or the like during peeling was observed.
After the boil sterilization treatment, the sample was placed in a light irradiation environment at 22 ° C. and 1600 lux and subjected to a storage test for one month. As a result, the discoloration and odor of the package contents were not observed.

[Comparative Example 1]
(1) First, the following resin compositions (a), (b), (c) and (d) were prepared.
(I) Resin composition constituting the first layer Functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) 100.0 parts by weight A resin composition constituting the first layer was prepared.
(B) Resin composition constituting the second layer 79.7 parts by weight of a functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) Rutile-type titanium content: 95%, Al ₂ O ₃ as a surface treatment agent: 20.0 parts by weight of titanium oxide pigment having a composition of 5%, and 1.0 part by weight of stearate ester as a pigment dispersant Thus, a resin composition constituting the second layer was prepared.
(C) Resin composition constituting the third layer 72.3 parts by weight of a functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) Rutile-type titanium pure content: 93%, Al ₂ O ₃ as a surface treating agent: 25.0 parts by weight of titanium oxide pigment having a composition of 5%, Benzpyrene-free carbon black 1.1 parts by weight as a black pigment, pigment dispersant As a result, 1.2 parts by weight of stearic acid ester was sufficiently kneaded to prepare a resin composition constituting the third layer.
(D) Resin composition constituting the fourth layer Functional polypropylene block polymer (PF380A manufactured by Sun Allomer Co., Ltd .: density = 0.9 / cm ³ , MFR = 1.0 g / 10 min) and 100.0 parts by weight were synthesized. A resin composition constituting the fourth layer was prepared by sufficiently kneading 0.5 part by weight of silica, 0.05 part by weight of erucic acid amide, and 0.05 part by weight of ethylene bisoleic acid amide.

(2) (4) Resin composition layer 10 μm, (b) Resin composition layer 20 μm, (C) Resin composition layer 10 μm, (4) A multi-layer unstretched olefin sealant having a total thickness of 70 μm composed of four resin composition layers of 30 μm was manufactured.
(3) Corona treatment is applied to the surface of the first layer of the multilayer non-stretched sealant, and a two-component curable urethane adhesive (main agent: polyester polyol, hardener: aliphatic isocyanate) is applied to the surface, and a stretched polyamide film (Unitika Emblem ONBC) 15 [mu] m was bonded, and then stretched polyester-based silica vapor deposited film (IB-PET-RB) 12 [mu] m was similarly bonded to the stretched polyamide-based film through a two-component urethane adhesive. A laminated film for packaging was produced.
(4) A four-sided pouch with a size of 130 mm × 170 mm was prepared from the produced laminated film for packaging using an impulse sealer, and was prepared from 15 g of butter, 15 g of flour, 200 ml of milk, salt and pepper in this pouch. 200 g of white sauce was filled and the mouth of the pouch was sealed. The sealed retort packaging bag was subjected to a retort sterilization treatment at 120 ° C. for 30 minutes to prepare a white sauce packaging bag for storage.
After a retort sterilization treatment, a storage test for one month was performed in a light irradiation environment at 37 ° C. and 1600 lux, and then an abnormal odor of white sauce was observed on the third day. Although no discoloration of the package contents was observed, it was difficult to continue the sensory test for odor evaluation.

[Experimental example]
Examples 1 to 5 and Comparative Example 1 were evaluated by measuring film thickness, oxygen permeability, total light transmittance, and odor evaluation.
(1) Measurement of film thickness This was measured from a μ-meter manufactured by Sony Corporation and a cross-sectional photograph.
(2) Oxygen permeability It measured with the measuring method based on JIS-K7126B method. After heat-treating each measurement sample, oxygen permeability was measured by the MOCON method under the condition of 23 ° C.-60% RH.
(3) Total light transmittance This was evaluated by measuring the transmittance of all light using a haze meter (SM-C) manufactured by Suga Test Instruments Co., Ltd.
(4) Evaluation of odor After storing various contents, a sensory test for 30 days was performed over time from 10 panelists.
The measurement results are shown in Table 1 below.

  As shown in Table 1, in Examples 1 to 5, no abnormal odor was observed over 30 days, but in Comparative Example 1, abnormal odor was observed on the third day of storage.

  According to the laminated film for packaging of the present invention, even if heat treatment such as boil sterilization or retort sterilization is performed, the odor of the contents does not change, and the packaging bag can sufficiently withstand long-term storage. Can be provided.

It is sectional drawing of the laminated | multilayer film for packaging of 1st embodiment of this invention. It is sectional drawing of the laminated film for packaging of 2nd embodiment of this invention. It is sectional drawing of the laminated film for packaging of 3rd embodiment of this invention. It is sectional drawing of the laminated film for packaging of 4th embodiment of this invention. It is sectional drawing of the laminated film for packaging of 5th embodiment of this invention. It is a top view of the pillow packaging bag which uses the laminated film for packaging of the present invention. It is a top view which shows the state which has arrange | positioned the high temperature softening resin to the elongate base film for the packaging bags for microwave ovens of Example 4. FIG. It is sectional drawing of the laminated film for packaging of Example 4. It is a top view of the packaging bag which uses the laminated film for packaging of Example 4.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base film 2 Multilayer unstretched sealant 2A Multilayer unstretched sealant 2B Multilayer unstretched sealant 2C Multilayer unstretched sealant 2D Multilayer unstretched sealant 2E Multilayer unstretched sealant 3a Transparent to translucent resin layer 3b Transparent to translucent resin layer 4 White Colored layer 4a White colored layer 4b White colored layer 5 Gray light-shielding layer 6 Black light-shielding layer 7 High-temperature softening resin layer 8 Print layer 9 Center seal part of pillow packaging bag 10a Lower seal part of pillow packaging bag 10b Upper seal of pillow packaging bag Part 11 Pillow packaging bag

Claims (10)

In a laminated film for packaging consisting of a base film and a multilayer unstretched olefin sealant,
At least one of the layers constituting the multilayer unstretched olefin sealant is a white colored layer formed by kneading and molding a polyolefin, a white pigment and a pigment dispersant,
Further, white pigment constituting the white colored layer, coated with rutile titanium, the surface of the rutile titanium, and SiO _2, and Al ₂ O _3, polio - consisting of a surface treatment agent comprising an Le A laminated film for packaging characterized by the above. The ratio of rutile type titanium, SiO ₂ , Al ₂ O ₃ and polyol constituting the white pigment is as follows: rutile type titanium (pure): 90 to 95 wt%, SiO ₂ : 3.5 to 5.0 wt%, Al ₂ O ₃ The laminated film for packaging according to claim 1, wherein: 2.0 to 3.5 wt%, polyol: 0 to 1.0 wt%. 2. The laminated film for packaging according to claim 1, wherein the white colored layer comprises polyolefin: 69 to 95 wt%, white pigment: 4 to 30 wt%, and pigment dispersant: 0.001 to 1.0 wt%. A gray shading layer is laminated adjacent to the white colored layer and opposite to the base film,
Furthermore, this gray shading layer is formed by kneading and molding polyolefin, white pigment, black pigment and pigment dispersant,
Further, white pigment constituting the gray shading layer is coated with rutile titanium, the surface of the particles of rutile titanium, and SiO _2, and Al ₂ O _3, polio - it from a surface treatment agent comprising an Le The
Furthermore, the ratio of rutile type titanium, SiO ₂ , Al ₂ O ₃ and polyol constituting the white pigment is such that the rutile type titanium (pure content): 90 to 95 wt%, SiO ₂ : 3.5 to 5.0 wt%, al ₂ O _3: 2.0~3.5wt%, polyol: packaging laminate film according to claim 1, characterized in that the 0~1.0wt%. The laminated film for packaging according to claim 4, further comprising a second white colored layer laminated adjacent to the gray light shielding layer. The laminated film for packaging according to claim 4 or 5, wherein the content of the white pigment in the gray light shielding layer is 5 to 30 times that of the black pigment. The laminated film for packaging according to claim 4 or 5, wherein a black light-shielding layer obtained by kneading and molding polyolefin, a black pigment and a pigment dispersant is laminated instead of the gray light-shielding layer. The laminated film for packaging according to any one of claims 4 to 7 , wherein the black pigment is benzpyrene-free carbon black having a benzpyrene concentration of 5 ppb or less. Polyolefins constituting each layer of the multi-layer unstretched olefin sealant are polypropylene, propylene-ethylenepropylene rubber block copolymer, propylene-ethylene random copolymer, high-pressure low-density polyethylene, ethylene-α-olefin copolymer, medium-density polyethylene. The laminated film for packaging according to any one of claims 1 to 7, comprising a combination of any two or more of olefin, high-density polyethylene, ethylene-vinyl acetate copolymer, and olefin. A packaging bag comprising the laminated film for packaging according to any one of claims 1 to 9.

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