JP2019123172A - Content-resistant high drop-bag strength laminate and packaging material and packaging bag using the laminate - Google Patents

Abstract

To provide a high drop-bag strength laminate for a packaging bag simultaneously having content resistance such as high-weight resistance, alcohol resistance, surfactant resistance, and acid/alkaline resistance, and a packaging material and a packaging bag using the laminate.SOLUTION: A content-resistant high drop-bag strength laminate 1 at least includes a substrate layer (A)2, a dry lamination adhesive layer 1(C)3, a metal element-containing barrier layer (D)5, a sealant layer (F)8 and a dry lamination adhesive layer 2(E)6. The dry lamination adhesive layer 2(E)6 is a layer formed from aqueous dispersion with an unsaturated carboxylic acid modified polyolefin resin dispersed therein, and is neighboring the sealant layer (F)8. The sealant layer (F)8 is a layer formed by laminating a film with a pressure device heated at 80-200°C.SELECTED DRAWING: Figure 1

Description

  TECHNICAL FIELD The present invention relates to a highly-dropable bag-strength laminated body for packaging bags having high content resistance, a packaging material using the laminate, and a packaging bag.

  In detail, as content resistance, specifically, high weight resistance, alcohol resistance, surfactant resistance, acid resistance, alkali resistance, spice resistance, oil resistance, organic solvent resistance, resistance Medicinal components are listed, and the contents are high weight, high alcohol content, high surfactant content, high pH, low pH, high spices content, high oil content, high organic solvent content, high A laminate for a packaging bag, which can maintain high drop strength without causing delamination even if the content of the medicinal ingredient is the content of the packaging bag filled with the contents, and a package using the laminate Regarding materials and packaging bags.

  Conventionally, for example, a base material layer, a barrier layer, a sealant layer (usually a polyolefin resin layer), and the like are used as packaging bags for sealing and packaging alcohol-containing substances, liquid detergents for refilling or shampoos or rinses, respectively. A packaging bag produced by heat-sealing a laminated body laminated through the above was used.

  However, there is no problem if the contents to be packaged are relatively low such as alcohol content of 50% by mass or less like alcohol, but if the alcohol concentration is higher than 50% by mass or liquid detergent In the case of highly permeable liquids such as shampoos and rinses, the alcohol component penetrates into the laminate or the component such as surfactant penetrates into the laminate during long-term storage, and in particular, the barrier As a result of attacking the adhesive layer between the layer and the sealant layer, there has been a problem that the sealant layer peels off from the barrier layer and the packaging bag is broken.

  As a method of laminating a sealant layer on the barrier layer, generally, an anchor coat (AC) layer is provided as an adhesive layer on the barrier layer surface, and a resin of the sealant layer is extrusion coated and laminated thereon, or a barrier A method is adopted in which a film of a sealant layer previously formed in a film form on the layer surface is laminated by a dry lamination method using an adhesive for dry lamination such as a two-component curing polyurethane adhesive as an adhesive layer. ing.

  And, as an anchor coat agent (hereinafter, described as an AC agent) to be used for the above-mentioned anchor coat layer, an organic titanium AC agent, an isocyanate AC agent (urethane), a polyethyleneimine AC agent, a polybutadiene AC agent, etc. AC agents are commercially available and used, but any of them is in a packaging bag in which the content resistance is insufficient for the high concentration alcohol and the contents such as the liquid detergent, shampoo and rinse, and the contents are sealed and packaged. When a storage test at 60 ° C. for about 2 to 4 weeks is performed as an accelerated test of the storage property, there is a problem that the sealant layer peels from the barrier layer. In addition, the method of extrusion laminating and laminating did not have sufficient adhesive strength between the extruded resin and the sealant, and did not have sufficient bag-falling strength when it was used as a package for containing heavy substances or liquids with large volumes.

Further, also when the sealant layer is attached to the barrier layer by the dry lamination method, the content resistance of the adhesive for dry lamination is insufficient, and there is a problem that the sealant layer peels off from the barrier layer by the storage test. .
Moreover, the said AC agent and the adhesive agent for dry lamination use the organic solvent for the coating liquid except for a part of thing, The problem of discharging the organic solvent at the time of application and having an adverse effect on the environment is also obtained. there were.

  As a means for solving such problems, in the method of extrusion-coating and laminating the resin of the sealant layer on the barrier layer, aluminum foil is used as a barrier layer without providing an anchor coat layer on the barrier layer surface, and aluminum A method of using an ethylene-methacrylic acid random copolymer (EMAA resin), which is believed to exhibit excellent adhesion to metals such as foil, as a resin for the sealant layer, and extruding it directly onto the aluminum foil surface for lamination As a result of producing the above-mentioned laminate and producing a packaging bag with the laminate, the sealant layer may peel off the barrier layer even if the content is sealed and packaged in the packaging bag and the storage test is carried out It was possible to produce a packaging bag having good adhesion.

  However, even with this packaging bag, although the peeling (delamination) of the sealant layer by the storage test can be prevented, the laminate strength itself of the sealant layer to the barrier layer is not always sufficient. Therefore, when opening the packaging bag, When the bag is torn by hand, an elongation fracture of the sealant layer occurs at the tearing end due to the peeling of the sealant layer, the tearing line is disturbed, and there is a problem that the tearability, that is, the tearability is not good.

  An aqueous dispersion in which a polyolefin copolymer resin containing 0.01 to 5% by mass of unsaturated carboxylic acid or its anhydride is dispersed to have a number average particle diameter as small as 1 μm or less, and the aqueous dispersion It is described that the coating film of the aqueous dispersion formed so as not to contain the non-volatile aqueous conversion aid in the body is excellent in water resistance (see, for example, Patent Documents 1 to 3).

  However, in Patent Document 1, the coating film of the polyolefin resin aqueous dispersion described is also excellent in the content resistance to the content, and in the production of a laminate used for a packaging bag, it is dry at the time of laminating the sealant layer. It has not been described at all that using this aqueous dispersion as a lamination adhesive it is possible to produce packaging bags which also have an excellent resistance to the above-mentioned contents.

  In Patent Document 2, although the coating film of the polyolefin resin aqueous dispersion described is described to be resistant to the content of high surfactant content, high weight resistance, alcohol resistance, acid resistance, The alkali resistance is not described.

  In Patent Document 3, although the coating film of the polyolefin resin aqueous dispersion described is described to be resistant to the content of high alcohol content, high weight resistance, surfactant resistance, acid resistance, The alkali resistance is not described.

Patent No. 3699935 gazette Patent No. 5029007 Patent No. 5415670 gazette

The present invention has been made to solve the above-mentioned problems, and its object is to provide a laminate for packaging bags having high drop resistance and having high content resistance, and the laminate. It is providing the used packaging material and a packaging bag.
Specific content resistance is to simultaneously provide high weight resistance, alcohol resistance, surfactant resistance, acid and alkali resistance, etc., and the content is high in weight, high in alcohol content, high in surface activity. Even if one or more of agent content rate, acidity, alkalinity, etc. are also used, the packaging bag filled with these contents can maintain high drop bag strength without causing delamination. Point to
In addition, it is easy to cut off when opening the packaging bag, and furthermore, it is possible to reduce the amount of organic solvent discharged when manufacturing a laminate, which is excellent in performance and use aptitude, and has little adverse effect on the environment. An object is to provide a packaging bag.

  The present inventors, as a result of various studies, have a specific layer structure made of a specific material, and a laminate subjected to a specific aging treatment, a packaging material using the laminate, a packaging bag, and the like. It is found that it can solve the problem.

And this invention is characterized by the following points.
1. At least a substrate layer (A), a dry lamination adhesive layer 1 (C), a metal element-containing barrier layer (D), a dry lamination adhesive layer 2 (E), and a sealant layer (F) Content resistance high drop bag strength laminate,
The dry lamination adhesive layer 2 (E) is a layer formed from an aqueous dispersion in which the unsaturated carboxylic acid-modified polyolefin resin is dispersed, and is adjacent to the sealant layer (F),
The sealant layer (F) is a layer formed by laminating films by a pressurizing device heated to 80 ° C. or more and 200 ° C. or less, and the content resistance high drop bag strength laminate.
2. The content-resistant high-drop bag strength laminate according to 1 above, further comprising a reinforcing layer (B).
3. The aqueous dispersion substantially does not contain a non-volatile aqueous conversion aid,
The number average particle diameter of the unsaturated carboxylic acid-modified polyolefin resin in the aqueous dispersion is 1 μm or less.
Content-resistant high drop bag strength laminate as described in 1 or 2 above.
4. The structure in which the unsaturated carboxylic acid-modified polyolefin resin is derived from unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is 0.01% by mass or more and 5% by mass in the total unsaturated carboxylic acid-modified polyolefin resin Content-resistant high-drop bag strength laminate according to 3 above, which contains at the following ratio.

5. 4. Content resistant high drop bag strength laminate according to any of the above 1 to 3, wherein the thickness of the dry lamination adhesive layer 2 (E) is 0.5 μm or more and 6 μm or less.
6. The metal element-containing barrier layer (D) is one or more selected from the group consisting of aluminum foil, aluminum vapor deposition film, aluminum oxide vapor deposition film, silicon oxide vapor deposition film, or any one of the above 1 to 5 Content resistance high drop bag strength laminate.
7. Dry lamination adhesive layer 2 (E) contains LDPE or LLDPE,
The sealant layer (F) contains LDPE or LLDPE
Content-resistant high drop bag strength laminate according to any one of 1 to 6 above.
8. The content resistance is selected from the group consisting of weight resistance, acid resistance, alkali resistance, alcohol resistance, surfactant resistance, spice resistance, oil resistance, organic solvent resistance, drug resistance component resistance, 11. Content-resistant high drop bag strength laminate according to any one of 1 to 7 above, which is one kind or two or more kinds.
9. A content-resistant high drop bag strength packaging material comprising the high-weight resistant laminate according to any one of 1 to 8 above.
10. A content resistant high drop resistance package made from the high weight resistant packaging material according to 9 above.

According to the present invention, it is possible to obtain a highly-dropable bag-strength laminated body for packaging bags, which is highly resistant to content, and a packaging material and a packaging bag using the laminate.
Furthermore, even if the content is one or two or more of high weight, high alcohol content, high surfactant content, acidity, alkalinity, etc., it is high without causing delamination. It is possible to obtain a laminate for a packaging bag, packaging material, and a packaging bag which can maintain the falling bag strength.
In addition, it is easy to cut off when opening the packaging bag, and furthermore, it is possible to reduce the amount of organic solvent discharged when manufacturing the laminate, and it is excellent in performance and use aptitude, as well as for the environment. Also, laminates, packaging materials and packaging bags with less adverse effects can be obtained.

It is a sectional view showing an example of a layered product concerning the present invention. It is an external view which shows an example of the packaging bag which concerns on this invention.

<Laminate>
The content / physical property high drop bag strength laminate of the present invention comprises at least a substrate layer (A), a dry lamination adhesive layer 1 (C), a metal element-containing barrier layer (D), and a dry lamination adhesive layer 2 (E) and a sealant layer (F). And furthermore, a reinforcement layer (B) can also be included as needed.
Here, the dry lamination adhesive layer 2 (E) is preferably adjacent to the sealant layer (F).

  And it is preferable that a sealant layer (F) is a layer which the film was laminated | stacked and formed with the pressurizing apparatus heated at 80 degreeC or more and 200 degrees C or less.

In addition to the above, the content-physical-property high drop-bag strength laminate of the present invention can also contain a layer of the same type or different type as described above, as long as the above-mentioned stacking order is not inhibited.
The layers included in the content / physical property high drop bag strength laminate of the present invention, the stacking order of the layers, and the like will be described below.

[Base material layer (A)]
The base material layer (A) may be a resin film or sheet generally used for a packaging material for packaging, a synthetic paper, or a film or sheet such as a paper base, and the tensile strength, bending strength, While being excellent in mechanical strength, such as impact strength, what is excellent in printability is preferred.
The base material layer (A) may be a single layer or may be composed of two or more layers. In the case of two or more layers, they may be layers of the same composition or layers of different compositions.
Moreover, it is preferable that it is a uniaxially or biaxially stretched resin film or sheet.

  Specific examples of the resin include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate; polyamide resins such as nylon 6, nylon 66, and MXD 6 (polymetaxylylene adipamide); Cellophane; polyolefin resin of polyethylene resin, polypropylene resin, acid-modified polyolefin resin; polystyrene resin; polyurethane resin; acetal resin; EVOH and the like.

Depending on the type of contents to be packaged and the use conditions such as heat treatment after filling, suitable ones can be freely selected and used, but among the above, polyester resins and polyamide resins are preferable. .
In particular, uniaxial or biaxially oriented polyethylene terephthalate film or sheet, biaxially oriented polypropylene film or sheet, etc. are suitable.

The resin film or sheet used for the substrate layer (A) is, if necessary, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidative property, slipperiness, releasability, flame retardancy Lubricants, crosslinking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, etc. for the purpose of improving and modifying the antifungal properties, electrical properties, strength, etc. Plastics additives, additives and the like can be added, and the amount thereof can be optionally added according to the purpose as long as other performance is not adversely affected.

  As a specific paper substrate, for example, strong-sized exposed or non-bleached paper substrate, or pure white roll paper, kraft paper, paperboard, coated paper, cast coated paper, processed paper, high-quality paper, etc. Can be used.

The film or sheet used for the base material layer (A) may be vapor-deposited with metal or metal oxide.
Moreover, the film or sheet which comprises a base material layer (A) and a base material layer (A) is a corona discharge treatment, ozone treatment, oxygen gas, nitrogen gas, etc. beforehand before lamination in order to improve adhesiveness. Physical treatments such as low temperature plasma treatment and glow discharge treatment using the above, and chemical treatments such as oxidation treatment using chemicals may be performed.

10 micrometers or more and 50 micrometers or less are preferable, and, as for the thickness of a base material layer (A), 15 micrometers or more and 40 micrometers or less are more preferable.
If the thickness is thinner than the above range, the rigidity of the laminate is too low to tend to exhibit high drop bag strength. If the thickness is thicker than the above range, the rigidity of the laminate becomes too high to process the laminate. It tends to be difficult, and the content fillability also tends to deteriorate.

[Reinforcement layer (B)]
The reinforcing layer (B) is a layer contained in the laminate if necessary, and is a layer responsible for reinforcement such as tensile strength, flexural strength, impact strength, puncture strength, breaking strength, toughness, rigidity, etc. By including B), it is possible to broaden the choice of the configuration of other layers such as the base material layer (A) and the sealant layer (F).
For the reinforcing layer (B), a uniaxial or biaxial stretched film or sheet of a known or commercially available resin similar to the substrate layer (A) can be used, depending on the kind of the contents to be packaged and the conditions of use. Any suitable one can be selected and used.
Among the above, uniaxially or biaxially stretched films or sheets of polybutylene terephthalate and polyamide resins, particularly nylon resins, are preferable.

The reinforcing layer (B) may be a single layer or may be composed of two or more layers. In the case of two or more layers, they may be layers of the same composition or layers of different compositions.
Furthermore, similarly to the base material layer (A), a metal or a metal oxide may be vapor-deposited, and may be pretreated to improve adhesion.

[Dry lamination adhesive layer 1 (C)]
Dry lamination adhesive layer 1 (C) is a layer which provides interlayer adhesiveness in a layered product.
The dry lamination adhesive layer 1 (C) can be formed using a known or commercially available dry lamination (DL) adhesive.
Specific examples of the dry lamination adhesive include a two-component curing polyurethane adhesive, a two-component curing polyester adhesive, a polyolefin-based (low density polyethylene, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer) And heat-adhesive resins such as unsaturated carboxylic acid-modified polyolefins and ionomers.

  Since the dry lamination adhesive layer 1 (C) is formed by dry lamination, it is possible to prevent the decrease in adhesion due to the occurrence of pinholes in the dry lamination adhesive layer (C). Moreover, the discharge amount of the organic solvent at the time of laminated body manufacture can be reduced, and the adverse effect on the environment can be reduced.

The dry lamination adhesive layer 1 (C) may be a single layer or may be composed of two or more layers. In the case of two or more layers, they may be layers of the same composition or layers of different compositions.
Moreover, the dry lamination adhesive layer 1 (C) of the same composition or a different composition may be laminated | stacked on two or more places in a laminated body.

[Metal Element-Containing Barrier Layer (D)]
The metal element-containing barrier layer (D) is a layer having a barrier property, and a metal foil, or a vapor-deposited film made of an inorganic substance or inorganic oxide containing a metal element can be used, and an aluminum foil, an aluminum vapor-deposited film, oxidation One or two or more selected from the group consisting of an aluminum vapor deposition film and a silicon oxide vapor deposition film are preferable, and in particular, an aluminum foil or an aluminum vapor deposition film is preferable.

The metal element-containing barrier layer (D) may be composed of one or more layers. When it comprises two or more layers, each layer may be the same composition, may be a different composition, and may not be laminated adjacently.
Here, the barrier property refers to the permeation blocking property to the outside of the contents, the gas barrier property, the light shielding property and the like, and is selected as necessary.
The ability to block the penetration of the contents to the outside can improve the preservation of the contents.

Specifically, the gas barrier properties include oxygen barrier properties, water vapor barrier properties and the like, and oxygen and water vapor infiltrate the packaging bag from the outside to deteriorate the contents, or the water inside the packaging bag goes to the outside of the packaging bag Can be prevented from being dissipated, and the preservation of the contents can be enhanced.
Specifically, the light blocking properties include visible light blocking properties, ultraviolet light blocking properties, and the like, and the deterioration of the contents due to light can be prevented, and the storage property of the contents can be enhanced.

  The thickness of the metal element-containing barrier layer (D) is preferably 15 nm to 20 μm. In the case of metal foil, 5 micrometers-20 micrometers are preferable, and 1 nm-20 micrometers are more preferable. In the case of the vapor deposition film, 15 to 200 nm is preferable, and the more preferable thickness varies depending on the vapor deposition species, but in the case of the aluminum vapor deposition film, 1 to 100 nm is more preferable, 15 to 60 nm is more preferable, 10 to 40 nm is particularly preferable . In the case of a silicon oxide vapor deposition film or an aluminum oxide vapor deposition film, 1 to 100 nm is more preferable, 10 to 50 nm is more preferable, and 20 to 30 nm is particularly preferable.

When the metal element-containing barrier layer (D) is a metal foil, the metal element-containing barrier layer (D) is formed of a dry lamination adhesive layer 1 (C) or a dry lamination adhesive layer 2 (E). It can be glued to the layer.
When the metal element-containing barrier layer (D) is a vapor deposition film, the metal element-containing barrier layer (D) can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, The composition and formation method are not particularly limited.

As a forming method, for example, physical vapor deposition (Physical Vapor Deposition, PVD) such as vacuum deposition, sputtering, and ion plating, or plasma chemical vapor deposition, thermal chemical vapor deposition, And chemical vapor deposition (chemical vapor deposition, CVD) such as photochemical vapor deposition.
When forming a deposition film, the surface to be deposited can be pretreated if necessary. Specifically, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow, etc. Physical treatment such as discharge treatment or chemical treatment such as oxidation treatment using chemicals or the like may be performed.

  When the metal element-containing barrier layer (D) is a vapor deposition film, it may be formed on the film or sheet constituting the base material layer (A) or the reinforcing layer (B), or biaxially stretched It may be formed on a film or sheet made of polyethylene terephthalate, polyacrylonitrile, ethylene-vinyl alcohol copolymer.

[Dry lamination adhesive layer 2 (E)]
The dry lamination adhesive layer 2 (E) is a layer which provides interlayer adhesion in the laminate, is a dry lamination adhesive layer adjacent to the sealant layer (F), and the sealant layer (F) is laminated in the laminate. Is a layer that plays a role in bonding to
Although it is possible to use an adhesive having the same composition as the dry lamination adhesive layer 2 (E) in a layer not adjacent to the sealant layer (F), in this case, the dry lamination adhesive layer 1 (C) are categorized.
By having the said structure, the laminated body has acquired favorable adhesiveness.

  The thickness of the dry lamination adhesive layer 2 (E) is preferably 0.05 μm or more and 2 μm or less. If it is thinner than the above range, the dry lamination adhesive layer 2 (E) tends to be inhomogeneous, and if it is thicker than the above range, pinhole voids etc. are easily generated in the dry lamination adhesive layer 2 (E). Adhesiveness is likely to be reduced.

The dry lamination adhesive layer 2 (E) is preferably a layer formed from an aqueous dispersion in which the unsaturated carboxylic acid-modified polyolefin resin is dispersed.
The dry lamination adhesive layer 2 (E) can be formed, for example, by applying the aqueous dispersion and drying at 80 to 120 ° C. or melt extrusion at 270 to 330 ° C.
By using the aqueous dispersion for the dry lamination adhesive layer 2 (E), the content resistance of the packaging bag is improved as compared with the case where a usual urethane anchor coating agent is used, and the interlayer adhesion by the contents is achieved. A reduction in strength can be prevented, delamination can be reduced, and a reduction in drop bag strength can be prevented.

The content of the unsaturated carboxylic acid-modified polyolefin-based resin in the aqueous dispersion is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, still more preferably 5 to 50% by mass, and 10 to 45% by mass Is particularly preferred. A good film formability can be obtained by setting the content to the above range.
Here, it is preferable that the aqueous dispersion substantially does not contain a non-volatile aqueous conversion aid. Thereby, the plasticization of the dry lamination adhesive layer 2 (E) can be prevented, the adhesive strength at the interface of the dry lamination adhesive layer 2 (E) can be increased, and the content resistance is improved.
The phrase "substantially free of non-volatile water-forming aid" means that the non-volatile water-forming aid is not positively added to the system, resulting in the absence of these materials. The content of the non-volatile aqueous conversion aid is particularly preferably zero, but it is, for example, less than 0.1% by mass with respect to the unsaturated carboxylic acid-modified polyolefin resin component within the range not impairing the effects of the present invention The degree may be included.

The main solvent of the aqueous dispersion is water, but water-soluble alcohols and ethers may be contained, and even if the resin component contains a small amount of organic solvent component added as a plasticizer or the like. Good.
Furthermore, if it is a volatile aqueous solution auxiliary agent, it may contain a small amount, for example, the unsaturated carboxylic acid modified polyolefin resin dispersed by containing a basic compound such as ammonia and a volatile organic amine compound The aggregation of the fine particles is prevented to provide stability.
Moreover, since the discharge amount of the harmful organic solvent at the time of laminated body manufacture can be reduced by using aqueous dispersion liquid, the bad influence with respect to the environment can also be decreased.

  The unsaturated carboxylic acid-modified polyolefin resin is dispersed in the form of fine particles in the aqueous dispersion, and the number average particle diameter of the fine particles is preferably 1 μm or less, and is 0.01 μm or more, 1 μm or more. It is more preferable that The weight average particle diameter is also preferably 1 μm or less, and more preferably 0.01 μm or more and 1 μm or less. If it is smaller than the above range, it becomes difficult to produce an aqueous dispersion and the process becomes complicated, so the cost tends to increase, and if it is larger than the above range, the dry lamination adhesive layer 2 (E ) Tends to be inhomogeneous, which may lower the adhesion.

(Unsaturated carboxylic acid modified polyolefin resin)
The polystyrene equivalent weight average molecular weight of the unsaturated carboxylic acid-modified polyolefin resin in the present invention is preferably 5,000 to 200,000, more preferably 10,000 to 150,000, and 20,000 It is more preferably -120,000, particularly preferably 30,000 to 100,000, and most preferably 35,000 to 80,000.
When the weight average molecular weight is less than the above range, the adhesion to the substrate tends to be reduced, and the resulting coating film tends to be hard or brittle. On the other hand, when the weight average molecular weight exceeds the above range, the resin Tend to be difficult to achieve.

An unsaturated carboxylic acid-modified polyolefin resin is a copolymer obtained by reacting an unsaturated carboxylic acid or a derivative thereof with an α-olefin, or a resin obtained by reacting a polyolefin with an unsaturated carboxylic acid or a derivative thereof, and a polyolefin resin It is a resin having a form in which unsaturated carboxylic acid is incorporated in the main chain or side chain of the resin, and a chemical bond is formed between the polyolefin resin and the unsaturated carboxylic acid.
The form of copolymerization is not limited, and examples thereof include random copolymerization, block copolymerization, graft copolymerization and the like. Further, it may be a binary copolymerization or a ternary or higher copolymerization.

The unsaturated carboxylic acid is a compound having one or more unsaturated bonds and one or more carboxyl groups in one molecule.
Specific examples of the unsaturated carboxylic acids include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid; and derivatives thereof Can be mentioned.
The derivatives of unsaturated carboxylic acids include chlorides, amides, esters and anhydrides of the above-mentioned acids, and in the case of unsaturated dicarboxylic acids, also half derivatives such as half esters and half amides.

Examples of esters of the above acids include methyl ester, ethyl ester, propyl ester and dimethylaminoethyl ester.
The polyolefin resin is a homopolymer or copolymer using one or more α-olefins as a raw material monomer.
Specific examples of the α-olefin include, for example, α-olefins having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms such as ethylene, propylene, isobutylene and hexene. Preferred α-olefins are ethylene and propylene.

Moreover, the copolymer which used together other monomers other than alpha-olefin as a monomer may be sufficient as polyolefin. Examples of such other monomers include vinyl ester monomers such as vinyl acetate.

  Specific examples of the polyolefin resin preferably used for the dry lamination adhesive layer 2 (E) include linear low density polyethylene (LLDPE), an ethylene-α-olefin copolymer polymerized using a single site catalyst, Polyethylene resins such as low density polyethylene (LDPE) and ionomers; polypropylene resins; polybutadiene resins, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers; unsaturated carboxylic acid-modified polyolefin resins, etc. Be

  The unsaturated carboxylic acid-modified polyolefin resin has a structure derived from unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in an amount of 0.01% by mass or more and 5% by mass or less in the total unsaturated carboxylic acid-modified polyolefin resin It is preferable to include in the ratio of If the amount is less than the above range, it is likely to be difficult to make the resin aqueous (liquid) and it becomes difficult to obtain a good aqueous dispersion. If the amount is more than the above range, the stability of the aqueous dispersion is reduced, and it becomes difficult to adjust the number average particle diameter of the unsaturated carboxylic acid-modified polyolefin resin in the aqueous dispersion to the above range. There is a risk of lowering the sex.

(Non-volatile water conversion aid)
In the present invention, the non-volatile aqueous conversion aid is a non-volatile drug or compound which is added for the purpose of promoting aqueous formation or stabilization of the aqueous dispersion in the production of the aqueous dispersion.
Here, non-volatile refers to having no boiling point at normal pressure or having a high boiling point (for example, 300 ° C. or more) at normal pressure.

Examples of the non-volatile aqueous conversion aid include compounds having a protective colloid action such as an emulsifier and a surfactant, modified waxes, acid-modified compounds with high acid value, water-soluble polymers and the like.
As an emulsifier, a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, or an amphoteric emulsifier is mentioned, In addition to what is generally used for emulsion polymerization, surfactant is also contained. For example, as an anionic emulsifier, sulfates of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinic acid And nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide Compounds having a polyoxyethylene structure such as a copolymer, and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid ester And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like.

Compounds having protective colloid action such as surfactants, modified waxes, acid-modified compounds with high acid value, and water-soluble polymers such as polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, Acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less such as modified starch, polyvinyl pyrrolidone, polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax Salts, acrylic acid-maleic anhydride copolymers and salts thereof, styrene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid copolymers, isobutyric acid Carboxyl group-containing polymers having unsaturated carboxylic acid content of 10% by mass or more and salts thereof, polyitaconic acid, and polymers such as acrylic acid / maleic anhydride alternating copolymer, (meth) acrylic acid / (meth) acrylic acid ester copolymer The salt, the water-soluble acrylic copolymer having an amino group, gelatin, gum arabic, casein and the like, compounds generally used as a dispersion stabilizer for fine particles can be mentioned.

[Sealant layer (F)]
The sealant layer (F) is a layer that imparts functions such as heat sealability, flex resistance and impact resistance to the laminate, and is adjacent to the dry lamination adhesive layer 2 (E) in the laminate. , And a layer laminated on the outermost layer of the laminate.
The sealant layer (F) may be a single layer or may be composed of two or more layers. In the case of two or more layers, they may be layers of the same composition or layers of different compositions. However, it is preferable that the layer which comprises the surface layer of a laminated body contains resin excellent in heat sealability.

  Specific examples of the resin include polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, metallocene polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, Ethylenic (meth) acrylate copolymer, ethylene (meth) acrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, anhydride Polyolefin resins modified with unsaturated carboxylic acids such as maleic acid, fumaric acid, etc., terpolymer resin of ethylene- (meth) acrylate-unsaturated carboxylic acid, cyclic polyolefin resin, cyclic olefin copolymer, polyethylene tee Phthalate (PET), polyacrylonitrile (PAN) and the like.

For the sealant layer (F), a resin film or sheet using one or more of the above resins, or a resin coating film or the like can be used.
If necessary, a known flex resistance improver, inorganic or organic additive and the like can be blended into the above resin.
As the film or sheet for forming the above resin layer, any of an unstretched film or sheet, or a stretched film or sheet stretched in a uniaxial direction or biaxial direction can be used.

Among the above, the sealant layer (F) preferably contains a polyolefin resin from the viewpoint of heat sealability and content resistance, more preferably LDPE or LLDPE, and particularly preferably LLDPE.
As a method of laminating the sealant layer (F), a method of extrusion laminating the resin composition for the sealant layer (F) on the dry lamination adhesive layer 2 (E), a resin film for the sealant layer (F) or The method of thermocompression-bonding a sheet | seat etc. is mentioned, The method of thermocompression-bonding the resin film or sheet for sealant layers (F) is preferable.

  It is preferable that said thermocompression bonding is performed by the pressurizing apparatus heated at 80 degreeC or more and 200 degrees C or less. If the temperature is lower than the above range, the effect of the thermocompression bonding tends to be difficult to be sufficiently expressed, and if the temperature is higher than the above range, various changes due to the thermocompression bonding are likely to rapidly progress, making the control complicated. And tend to be less productive.

  By laminating the sealant layer (F) according to the above-mentioned method, the laminate strength of each layer interface in the content resistant high drop bag strength laminate, in particular the laminate strength of the sealant layer (F), of the layer laminated by extrusion lamination Even the interface is improved, and in particular, the laminate strength of the dry lamination adhesive layer 2 (E) interface is improved, and the packaging bag can sufficiently withstand the high weight of the contents.

Furthermore, the strength of the laminate is not only improved, but the contents of the packaging bag may be alcohol-containing substances, acidic substances or alkaline substances, and the contents may be stored for a long time in the filled state. Good laminate strength, and the content resistance of the packaging bag is improved.
And, by improving the laminate strength, the drop impact resistance of the filling of the packaging bag is improved.
In addition, it is possible to prevent the low manual opening property due to the peeling of the sealant layer (F) at the time of manual opening after long-term storage.

  5-500 micrometers is preferable, as for the thickness of a sealant layer (F), 10-250 micrometers is more preferable, and 15-100 micrometers is still more preferable. If the thickness is thinner than the above range, it is difficult to obtain sufficient heat seal strength. If the thickness is larger than the above range, the cost increases and the film becomes hard, and the workability tends to be deteriorated.

<Content-resistant physical property>
The content property resistance in the present invention includes, for example, weight resistance property, acid resistance, alkali resistance, alcohol resistance, surfactant resistance, spice resistance, oil resistance, organic solvent resistance, medicinal component resistance and the like. High weight, strong acidity, strong alkalinity, high alcohol content, high surfactant content, high spice content, oiliness, organic solvent content, high efficacy ingredients (limonene, menthol etc.) content It shows that the laminate, the packaging material and the package have resistance to the contents of the above.

The laminate, the packaging material, and the packaging bag according to the present invention have one or more of the group consisting of the various content resistances described above.
If the content resistance to physical properties is insufficient, the laminate, the packaging material, and the package may cause delamination, breakage, or hand-open failure.

<Packaging material>
The content-resistant high drop-bag strength packaging material of the present invention comprises the above-mentioned content-resistant high drop-bag strength laminate.

<Packaging bag>
The content resistant property high drop bag strength packaging bag of the present invention can be manufactured by heat sealing the above-mentioned content resistant property high drop bag strength packaging material in the form of a bag.

  The aspect of the packaging bag according to the present invention is not particularly limited, and, for example, flat bags such as three-sided sealing type or four-sided sealing type, or pillow type bags, free standing bags such as standing pouch, and gusset bags Or the packaging bag of any aspect, such as these application forms may be sufficient.

Raw materials used in the examples are as follows.
PET film 1: A biaxially stretched PET film manufactured by Toyobo Co., Ltd., T-4102. One side corona treatment. 12 μm thick.
PET film 2: A biaxially stretched PET film with a single-sided aluminum vapor deposition film manufactured by Toray Film Co., Ltd. 12 μm thick. Aluminum deposition thickness 40 nm.
PBT film 1: A biaxially stretched PBT film manufactured by Kojin Film & Chemicals Co., Ltd., Boblet ST. One side corona treatment. 15 μm thick.
Nylon film 1: Biaxially stretched nylon film manufactured by Toyobo Co., Ltd., Harden film N1200. Two-sided corona treatment. Thickness 15 μm.
Nylon film 2: A biaxially stretched nylon film manufactured by Toyobo Co., Ltd., Harden film N7476, 15 μm thick. Single sided aluminum deposition.
Polyethylene-based resin 1: Linear low density polyethylene, SP1 manufactured by Prime Polymer Co., Ltd.
071C. MFR 10 g / 10 min.
LLDPE film 1: manufactured by Mitsui Chemicals Toshiro Co., Ltd. T. U. X-HC. 100 μm thick.
Aluminum foil 1: 1N30 manufactured by Toyo Aluminum Co., Ltd. 7 μm thick.
DL adhesive 1: Two-component curable polyurethane adhesive manufactured by Toyo Morton, TM-570 / CAT-RT37 = weight ratio 18/1
DL adhesive 2: Arrow base manufactured by Unitika Co., Ltd. Aqueous dispersion of unsaturated carboxylic acid modified polyolefin resin.

Example 1
The PET film 1 as the base material layer (A) and the nylon film 1 as the reinforcing layer (B) are laminated by dry lamination via the DL adhesive 1 as the dry lamination adhesive layer 1 (C) Furthermore, the nylon film surface and the aluminum foil 1 as the metal element-containing barrier layer (D) were laminated by dry lamination via the DL adhesive 1.
Then, DL adhesive 2 as dry lamination adhesive layer 2 (E) was applied to the aluminum foil surface in an amount such that the weight after drying was 3 g / m ² , and dried to obtain laminate A.

  Next, the LLDPE film 1 as a sealant layer (F) was stacked on the DL adhesive 2 side of the laminate A, and thermocompression bonding was performed at 100 ° C. by a laminating nip roller to obtain a laminate.

Layer configuration of laminate: PET film 1 (12 μm) / DL adhesive 1 (3 μm) / nylon film 1 (15 μm) / DL adhesive 1 (3 μm) / aluminum foil 1 (7 μm) / DL adhesive 2 (3 g /) m ² ) / LDPE film 1 (100 μm)
Various evaluations were performed using the obtained laminated body. The results are shown in Table 1.

Example 2
A laminate was obtained and operated in the same manner as in Example 1 except that the temperature of thermocompression bonding was changed to 120 ° C., and evaluated in the same manner. The results are shown in Table 1.

[Example 3]
A laminate was obtained and operated in the same manner as in Example 1 except that the temperature of thermocompression bonding was changed to 150 ° C., and evaluated in the same manner. The results are shown in Table 1.

Example 4
The PET film 1 as the base material layer (A) and the nylon film 1 as the reinforcing layer (B) are laminated by dry lamination via the DL adhesive 1 as the dry lamination adhesive layer 1 (C) Furthermore, the nylon film surface and the aluminum foil 1 as the metal element-containing barrier layer (D) were laminated by dry lamination via the DL adhesive 1.
Then, DL adhesive 2 as dry lamination adhesive layer 1 (C) was applied to the aluminum foil surface in an amount such that the weight after drying was 3 g / m ² and dried.
Next, the PET film 1 as a reinforcing layer (B) was overlaid on the DL adhesive 2 side, and thermocompression bonding was performed at 120 ° C. by a laminating nip roller to obtain a laminate A.

Layer configuration of laminate A: PET film 1 (12 μm) / DL adhesive 1 (3 μm) / nylon film 1 (15 μm) / DL adhesive 1 (3 μm) / aluminum foil 1 (7 μm) / DL adhesive 2 (3 g) / M ² ) / PET film 1 (12 μm)

The amount of the DL adhesive 2 as the dry lamination adhesive layer 2 (E) on the surface of the PET film as the reinforcing layer (B) of the obtained laminate A, the weight after drying being 3 g / m ² And dried, and then, LLDPE film 1 as a sealant layer (F) was superposed on the DL adhesive 2 side, and thermocompression-bonded at 120 ° C. by a laminating nip roller to obtain a laminate.

Layer configuration of laminate: PET film 1 (12 μm) / DL adhesive 1 (3 μm) / nylon film 1 (15 μm) / DL adhesive 1 (3 μm) / aluminum foil 1 (7 μm) / DL adhesive 2 (3 g /) m ² ) / PET film 1 (12 μm) / DL adhesive 2 (3 g / m ² ) / LLDPE film 1 (100 μm)
It evaluated similarly to Example 1 using the obtained laminated body. The results are shown in Table 1.

[Example 5]
Dry the PET film 2 including the aluminum vapor deposited film as the base material layer (A) and the nylon film 1 as the reinforcing layer (B) through the DL adhesive 1 as the dry lamination adhesive layer 1 (C) Lamination is performed by lamination, and further, DL adhesive 2 as dry lamination adhesive layer 2 (E) is applied to the nylon film surface by an amount such that the weight after drying is 3 g / m ² , and dried, Next, the LLDPE film 1 as a sealant layer (F) was superimposed on the DL adhesive 2 side, and thermocompression bonding was performed at 120 ° C. by a laminating nip roller to obtain a laminate.

Layer configuration of laminate: PET film 2 (12 μm) / aluminum deposited film (40 nm) / DL adhesive 1 (3 μm) / nylon film 1 (15 μm) / DL adhesive 2 (3 g / m ² ) / LLDPE film 1 ( 100 μm)
It evaluated similarly to Example 1 using the obtained laminated body. The results are shown in Table 1.

[Examples 6, 7]
A laminate was obtained in the same manner as in Example 2 except that the thickness of the dry lamination adhesive layer 2 (E) was changed to the thickness shown in Table 1, and was evaluated in the same manner. The results are shown in Table 1.

[Example 8]
A PET film 1 as a base material layer (A) was changed to a PBT film 1, and a reinforcing layer (B) and a dry lamination adhesive layer (C) for laminating the reinforcing layer (B) were not provided. A laminate was obtained and operated in the same manner as in Example 2 except for the same evaluation. The results are shown in Table 1.

Comparative Examples 1 to 3
A laminate was obtained and evaluated in the same manner as in Examples 2, 4 and 5 except that DL adhesive 2 was changed to DL adhesive 1. The results are shown in Table 1.
<Evaluation method>

[Lamination strength]
A strip-shaped test piece with a width of 15 mm is cut out from the laminate, and approximately 10 mm of the terminal short side of the test piece is peeled off with the adhesive layer adjacent to the sealant layer (F) interposed between them. The maximum load at the time of peeling was measured by a T-shaped peeling method (tensile speed 50 mm / min) in an atmosphere of 25 ° C. using an Orientec RTC-1310A) to obtain a laminate strength (N / 15 mm width). Furthermore, the peeling interface site was confirmed. The notations in Table 1 have the following meanings. The lamination strength passed 3N / 15 mm or more.
In the table, “non-peelable” indicates that the laminate strength was too strong to be peeled, and “already peeled” indicates that the peel was already peeled off before the peel test.

[Content resistance]
Three sides of the laminate were heat sealed to prepare a bag, and after filling and sealing the contents, it was stored at 40 ° C. for 7 days for 1 month, and the content resistance was evaluated by the decrease in laminate strength.

[Falling impact resistance]
Using the laminate, the gusset bag shown in FIG. 2 was produced with the following dimensions, filled with 500 ml of water, degassed and sealed to produce a test piece.
Then, after storing at 3 ° C. for 24 hours, the test specimen is dropped 10 times from the height of 1.2 m in the horizontal orientation from the height of 1.2 m, and then dropped 10 times in the vertical orientation, with or without water leakage Detected a defect.
The full width of the bag: 135 mm
Total length of bag: 225 mm
Folding length of bottom gusset part 14: 37 mm
Width of the largest part of the outlet seal part 17: 40 mm
Maximum length of the outlet seal part 17: 55 mm
The full width of the position where the half cut line 21 was provided: 24 mm
The tapering angle of the outlet 20: approximately 36 °
Method of preparing the half cut line 21: Laser light irradiation Half cut line interval: 0.7 mm
Half cut line depth: about 30 μm

[Evaluation result summary]
The laminates of Examples 1 to 8 of the present invention exhibited strong laminate strength and content resistance, and the packaging bag made from the laminate exhibited strong drop impact resistance.
However, Comparative Examples 1 to 3 having no dry lamination adhesive layer 2 (E) adjacent to the sealant layer (F) showed inferior results.

1 Content resistance High drop bag strength laminate 2 Base layer (A)
3 Dry lamination adhesive layer 1 (C)
4 Reinforcement layer (B)
5 Metal Element Containing Barrier Layer (D)
6 Dry lamination adhesive layer 2 (E)
8 Sealant layer (F)
DESCRIPTION OF SYMBOLS 10 gusset bag 11, 11 'wall film 12 bottom film film-turned part 13a, 13b bottom film notch part 14 gusset part 15 bottom part seal part 16a, 16b side seal part 17 spout part seal part 18 upper seal part 19a, 19b cutting Notch 20 Injection port 21 Half cut 22 Notch

Claims (10)

At least a substrate layer (A), a dry lamination adhesive layer 1 (C), a metal element-containing barrier layer (D), a dry lamination adhesive layer 2 (E), and a sealant layer (F) Content resistance high drop bag strength laminate,
The dry lamination adhesive layer 2 (E) is a layer formed from an aqueous dispersion in which the unsaturated carboxylic acid-modified polyolefin resin is dispersed, and is adjacent to the sealant layer (F),
The sealant layer (F) is a layer formed by laminating films by a pressurizing device heated to 80 ° C. or more and 200 ° C. or less, and the content resistance high drop bag strength laminate.   The laminate according to claim 1, further comprising a reinforcing layer (B). The aqueous dispersion substantially does not contain a non-volatile aqueous conversion aid,
The number average particle diameter of the unsaturated carboxylic acid-modified polyolefin resin in the aqueous dispersion is 1 μm or less.
The content resistance high drop bag strength laminate according to claim 1 or 2.   The structure in which the unsaturated carboxylic acid-modified polyolefin resin is derived from unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is 0.01% by mass or more and 5% by mass in the total unsaturated carboxylic acid-modified polyolefin resin The content-resistant high-drop bag strength laminate according to claim 3, wherein the content ratio is as follows.   The content resistance high drop bag strength laminate according to any one of claims 1 to 3, wherein the thickness of the dry lamination adhesive layer 2 (E) is 0.5 μm or more and 6 μm or less.   The metal element-containing barrier layer (D) is one or more selected from the group consisting of an aluminum foil, an aluminum vapor deposition film, an aluminum oxide vapor deposition film, and a silicon oxide vapor deposition film. Content-resistant high drop bag strength laminate according to the item. Dry lamination adhesive layer 2 (E) contains LDPE or LLDPE,
The sealant layer (F) contains LDPE or LLDPE
The content resistant high drop bag strength laminate according to any one of claims 1 to 6.   The content resistance is selected from the group consisting of weight resistance, acid resistance, alkali resistance, alcohol resistance, surfactant resistance, spice resistance, oil resistance, organic solvent resistance, drug resistance component resistance, The content resistant high drop bag strength laminate according to any one of claims 1 to 7, which is one kind or two or more kinds.   A content resistant high drop bag strength packaging material comprising the high weight resistant laminate according to any one of claims 1 to 8.   A content resistant high drop bag strength packaging bag made from the high weight resistant packaging material body according to claim 9.

Images