JP7059642B2 - Content resistance High drop bag strength laminated body and packaging materials and packaging bags using the laminated body - Google Patents

Description

The present invention relates to a laminate having high content resistance, high bag strength, and high bag strength for packaging bags, and packaging materials and packaging bags using the laminate.

Specifically, the content resistance includes high weight resistance, alcohol resistance, surfactant resistance, acid resistance, alkali resistance, spice resistance, oil resistance, organic solvent resistance, and resistance to organic solvents. The contents include high weight, high alcohol content, high surfactant content, high pH, low pH, high spice content, high oil content, high organic solvent content, high content. Even if the content of the medicinal component is high, the packaging bag filled with these contents can maintain high drop-off strength without causing delamination, and the laminate for the packaging bag and the packaging using the laminate. Regarding materials and packaging bags.

Conventionally, as a packaging bag for sealing and packaging an alcohol-containing substance, a liquid detergent for refilling, shampoo, or a rinse, for example, a base material layer, a barrier layer, a sealant layer (usually a polyolefin resin layer), or the like is used as an adhesive layer. A packaging bag made by heat-sealing a laminated body laminated through the above was used.

However, there is no problem when the contents to be packaged are relatively low such as alcoholic beverages having an alcohol concentration of 50% by mass or less, but there is no problem when the alcohol concentration is high such as 50% by mass or more or a liquid detergent. In the case of highly permeable liquids such as shampoos and rinses, alcohol components may permeate the laminate or components such as surfactants may permeate the laminate during long-term storage, especially as a barrier. As a result of invading the adhesive layer between the layers and the sealant layer, there is a problem that the sealant layer is separated (delaminated) from the barrier layer and the packaging bag is damaged.

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

The anchor coating agent (hereinafter, also referred to as AC agent) used for the anchor coat layer includes an organic titanium-based AC agent, an isocyanate-based AC agent (urethane-based), a polyethyleneimine-based AC agent, a polybutadiene-based AC agent, and the like. AC agents are commercially available, but all of them lack the content resistance to the contents such as the high-concentration alcohol, the liquid detergent, shampoo, and rinse, and the contents are sealed and packaged in the packaging bag. As a storage test for promoting storage, there was a problem that the sealant layer was peeled off from the barrier layer when the storage test was performed at 60 ° C. for about 2 to 4 weeks. Further, the method of extruding and laminating and laminating does not have sufficient adhesive strength between the extruded resin and the sealant, and does not have sufficient bag-dropping strength when a package containing a heavy object or a liquid having a large volume is used.

Similarly, when the sealant layer is attached to the barrier layer by the dry lamination method, the content resistance of the dry laminating adhesive is insufficient, and there is a problem that the sealant layer is peeled off from the barrier layer by the storage test. ..
In addition, the AC agent and the adhesive for dry laminating use an organic solvent as the coating liquid except for some of them, and there is a problem that the organic solvent is discharged at the time of application and adversely affects the environment. there were.

As a means for solving such a problem, in the method of extruding and coating the resin of the sealant layer on the barrier layer and laminating it, aluminum foil is used as the barrier layer without providing the anchor coat layer on the barrier layer surface, and aluminum is used. A method of using a random copolymer of ethylene-methacrylic acid (EMAA resin), which is said to have excellent adhesion to metals such as foil, as the resin of the sealant layer, and extruding it directly onto the aluminum foil surface for laminating. As a result of producing the laminate and producing a packaging bag from the laminate, the sealant layer may be peeled off from the barrier layer even if the contents are hermetically sealed and packaged in the packaging bag and the storage test is performed. It was possible to produce a packaging bag having good adhesiveness.

However, even with this packaging bag, although the peeling (delamination) of the sealant layer by the storage test can be prevented, the lamination strength of the sealant layer with respect to the barrier layer itself is not always sufficient, and therefore, when opening the packaging bag, When the bag is torn by hand, the sealant layer is stretched and broken at the torn end due to the peeling of the sealant layer, the tear line is disturbed, and there is a problem that the tearability, that is, the hand-cutting property is not good.

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

However, in Patent Document 1, the coating film of the described polyolefin resin aqueous dispersion is also excellent in the content resistance to the contents, and in the production of the laminate used for the packaging bag, it is dry when the sealant layer is laminated. There is no description that this aqueous dispersion can be used as a lamination adhesive to produce a packaging bag having excellent resistance to the above-mentioned contents.

In Patent Document 2, the coating film of the described polyolefin resin aqueous dispersion is described as having a high surfactant content resistance to the contents, but has high weight resistance, alcohol resistance, and acid resistance. Alkali resistance is not described.

In Patent Document 3, the coating film of the described polyolefin resin aqueous dispersion is described as having resistance to the contents having a high alcohol content, but has high weight resistance, surfactant resistance, and acid resistance. Alcohol resistance is not described.

Japanese Patent No. 369935 Japanese Patent No. 5029007 Japanese Patent No. 5415670

The present invention has been made to solve the above-mentioned problems, and the problem is to obtain a laminated body for a packaging bag having high content resistance and high drop bag strength, and the laminated body. It is to provide the used packaging material and packaging bag.
Specific content resistance is to have high weight resistance, alcohol resistance, surfactant resistance, acid / alkali resistance, etc. at the same time, and the content has high weight, high alcohol content, and high surface activity. Even if one or more of the agent content, acidity, alkalinity, etc. are combined, the packaging bag filled with these contents can maintain high drop-off strength without causing delamination. Point to.
In addition, it is easy to cut when opening the packaging bag, and the amount of organic solvent discharged when manufacturing the laminate can be reduced, which is excellent in performance and usability, and has little adverse effect on the environment. The subject is to provide packaging bags.

As a result of various studies, the present inventors have found a laminate having a specific layer structure made of a specific material and subjected to a specific aging treatment, and a packaging material and a packaging bag using the laminate. It was found that the problem could be solved.

The present invention is characterized by the following points.
1. 1. At least, it contains a base material 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). It is a laminated body with high content resistance and high drop bag strength.
The dry lamination adhesive layer 2 (E) is a layer formed from an aqueous dispersion in which an 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 higher and 200 ° C. or lower.
2. 2. Further, the content-resistant high-drop bag strength laminate according to 1 above, which includes a reinforcing layer (B).
3. 3. The aqueous dispersion is substantially free of the non-volatile aqueous aid.
The number average particle size of the unsaturated carboxylic acid-modified polyolefin resin in the aqueous dispersion is 1 μm or less.
The high-strength laminate with high content resistance and drop bag according to 1 or 2 above.
4. The unsaturated carboxylic acid-modified polyolefin resin has a structure derived from the unsaturated carboxylic acid or the unsaturated carboxylic acid anhydride in 0.01% by mass or more and 5% by mass in the total unsaturated carboxylic acid-modified polyolefin resin. The high content resistance high drop bag strength laminate according to 3 above, which is contained in the following proportions.

5. The high-strength laminate with high content resistance according to any one of 1 to 3 above, wherein the amount of the dry lamination adhesive layer 2 (E) applied is 0.5 g / m ² or more and 6 g / m ² or less. ..
6. 1. Highly resistant laminate with high drop bag strength.
7. The high content-resistant high-drop bag strength laminate according to any one of 1 to 6 above, wherein the dry lamination adhesive layer 2 (E) contains LDPE or LLDPE, and the sealant layer (F) contains LDPE or LLDPE.
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, and chemical resistance component resistance. The laminate having high content resistance and high drop bag strength according to any one of 1 to 7 above, which is one kind or two or more kinds.
9. A high-weight drop-resistant packaging material having a high content resistance and a high weight drop resistance according to any one of 1 to 8 above.
10. Content-resistant high-drop bag strength packaging bag made from the high-weight-resistant packaging material described in 9 above.

According to the present invention, it is possible to obtain a laminate having high content resistance, high bag strength, and high bag strength for packaging bags, and packaging materials and packaging bags using the laminate.
Furthermore, even if the content has one or more of high weight, high alcohol content, high surfactant content, acidity, alkalinity, etc., it does not cause delamination and is high. It is possible to obtain a laminate, a packaging material, and a packaging bag for a packaging bag that can maintain the bag-dropping strength.
In addition, it has good hand-cutting property when opening the packaging bag, and it is possible to reduce the amount of organic solvent discharged when manufacturing the laminate, which is excellent in performance and usability, and is environmentally friendly. It is possible to obtain a laminate, a packaging material, and a packaging bag with less adverse effects.

It is sectional drawing which shows an example of the laminated body which concerns on this invention. It is an external view which shows an example of the packaging bag which concerns on this invention.

<Laminated body>
The content-resistant and high-drop strength laminate of the present invention has at least a base material 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 the sealant layer (F) are included. Further, if necessary, the reinforcing layer (B) may be included.
Here, it is preferable that the dry lamination adhesive layer 2 (E) is adjacent to the sealant layer (F).

The sealant layer (F) is preferably a layer formed by laminating films by a pressurizing device heated to 80 ° C. or higher and 200 ° C. or lower.

If necessary, the content-resistant high-drop bag strength laminate of the present invention may contain layers of the same type or different types as those described above, as long as they do not interfere with the stacking order.
Each layer included in the content-resistant high-drop bag strength laminate of the present invention, the stacking order of each layer, and the like will be described below.

[Base material layer (A)]
As the base material layer (A), a resin film or sheet generally used as a packaging material for packaging bags, synthetic paper, a film or sheet such as a paper base material can be used, and tensile strength, bending strength, etc. Those having excellent mechanical strength such as impact strength and excellent printability are preferable.
The base material layer (A) may be one layer or may be composed of two or more layers. In the case of two or more layers, it may be a layer having the same composition or a layer having a different composition.
Further, it is preferably a uniaxially or biaxially stretched resin film or sheet.

Specific resins include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; polyamide resins such as nylon 6, nylon 66, and MXD6 (polymethoxylylen adipamide); Examples thereof include cellophane; polyethylene-based resin, polypropylene-based resin, polyolefin-based resin of acid-modified polyolefin-based resin; polystyrene-based resin; polyurethane-based resin; acetal-based resin; EVOH and the like.

A suitable material can be freely selected and used according to the type of contents to be packaged and the usage conditions such as the presence or absence of heat treatment after filling, but among the above, polyester-based resin and polyamide-based resin are preferable. ..
In particular, a uniaxially stretched polyethylene terephthalate film or sheet, a biaxially stretched polypropylene film or sheet, or the like is suitable.

The resin film or sheet used for the base material layer (A) has workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant property, slipperiness, releasability, and flame retardancy, if necessary. , Antifungal properties, electrical properties, strength, etc. for the purpose of improving and modifying lubricants, cross-linking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, etc. A plastic compounding agent, an additive, or the like can be added, and the amount thereof can be arbitrarily added as long as it does not adversely affect other performance.

Specific paper base materials include, for example, strong-sized bleached or unbleached paper base materials, pure white roll paper, kraft paper, paperboard, coated paper, cast-coated paper, processed paper, high-quality paper, and the like. Can be used.

The film or sheet used for the base material layer (A) may be vapor-deposited with a metal or a metal oxide.
In addition, the film or sheet constituting the base material layer (A) and the base material layer (A) is previously subjected to corona discharge treatment, ozone treatment, oxygen gas, nitrogen gas, etc. before laminating in order to improve adhesion. It may be subjected to physical treatment such as low temperature plasma treatment and glow discharge treatment using the above, and chemical treatment such as oxidation treatment using chemicals.

The thickness of the base material layer (A) is preferably 10 μm or more and 50 μm or less, and more preferably 15 μm or more and 40 μm or less.
If it is thinner than the above range, the rigidity of the laminated body is too low and it tends to be difficult to exhibit high bag strength. If it is thicker than the above range, the rigidity of the laminated body becomes too high and the laminated body is processed. It tends to be difficult and the filling property of the contents tends to deteriorate.

[Reinforcing layer (B)]
The reinforcing layer (B) is a layer included in the laminated body as needed, and is a layer responsible for reinforcement of tensile strength, bending strength, impact strength, piercing strength, breaking strength, toughness, rigidity, etc., and is a reinforcing layer (reinforcing layer). By including B), it is possible to expand the options for the configuration of other layers such as the base material layer (A) and the sealant layer (F).
As the reinforcing layer (B), the same known or commercially available resin uniaxial or biaxially stretched film or sheet as the substrate layer (A) can be used, depending on the type of contents to be packaged and the conditions of use. , You can freely select and use the suitable one.
Among the above, polybutylene terephthalate and uniaxial or biaxially stretched films or sheets of polyamide-based resins, particularly nylon-based resins are suitable.

The reinforcing layer (B) may be one layer or may be composed of two or more layers. In the case of two or more layers, it may be a layer having the same composition or a layer having a different composition.
Further, similarly to the base material layer (A), a metal or a metal oxide may be vapor-deposited, or a pretreatment for improving the adhesion may be performed.

[Dry lamination adhesive layer 1 (C)]
The dry lamination adhesive layer 1 (C) is a layer that imparts interlayer adhesiveness in the laminated body.
The dry lamination adhesive layer 1 (C) can be formed by using a known or commercially available dry lamination (DL) adhesive.
Specific examples of the dry lamination adhesive include a two-component curable polyurethane adhesive, a two-component curable polyester adhesive, and a polyolefin-based (low-density polyethylene, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer). , Unsaturated carboxylic acid-modified polyolefin, ionomer, etc.), heat-adhesive resin and the like.

Since the dry lamination adhesive layer 1 (C) is formed by dry lamination, it is possible to prevent deterioration of the adhesiveness due to the generation of pinhole voids in the dry lamination adhesive layer (C). In addition, the amount of organic solvent discharged during the production of the laminate can be reduced, and the adverse effect on the environment can be reduced.

The dry lamination adhesive layer 1 (C) may be one layer or may be composed of two or more layers. In the case of two or more layers, it may be a layer having the same composition or a layer having a different composition.
Further, the dry lamination adhesive layer 1 (C) having the same composition or a different composition may be laminated at two or more places in the 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 an inorganic oxide containing a metal element can be used, and an aluminum foil, an aluminum vapor-deposited film, or an oxidation film can be used. One or more selected from the group consisting of an aluminum vapor-deposited film and a silicon oxide vapor-deposited film is preferable, and an aluminum foil or an aluminum-deposited film is particularly preferable.

Further, the metal element-containing barrier layer (D) may be composed of one layer or two or more layers. When composed of two or more layers, each layer may have the same composition, may have a different composition, or may not be laminated adjacent to each other.
Here, the barrier property refers to the permeation blocking property, the gas barrier property, the light blocking property, etc. of the contents to the outside, and is selected as necessary.
The storage stability of the contents can be enhanced by the permeation blocking property of the contents to the outside.

Specific examples of the gas barrier property include oxygen barrier property and water vapor barrier property. Oxygen and water vapor infiltrate into the packaging bag from the outside to deteriorate the contents, and moisture inside the packaging bag moves to the outside of the packaging bag. It is possible to prevent it from being dissipated, and it is possible to improve the storage stability of the contents.
Specific examples of the light-shielding property include visible light light-shielding property, ultraviolet light-shielding property, and the like, deterioration of the content due to light can be prevented, and the storage stability of the content can be improved.

The thickness of the metal element-containing barrier layer (D) is preferably 15 nm to 20 μm. In the case of a metal foil, 5 μm to 20 μm is preferable, and 1 nm to 20 μm is more preferable. In the case of a thin-film deposition film, 15 to 200 nm is preferable, and the more preferable thickness varies depending on the vapor-deposited species, but in the case of an aluminum-deposited film, 1 to 100 nm is more preferable, 15 to 60 nm is more preferable, and 10 to 40 nm is particularly preferable. .. In the case of a silicon oxide-deposited film or an aluminum oxide-deposited film, 1 to 100 nm is more preferable, 10 to 50 nm is further 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 placed through the dry lamination adhesive layer 1 (C) and the dry lamination adhesive layer 2 (E). Can be glued to layers.
When the metal element-containing barrier layer (D) is a thin-film 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 an inorganic oxide. The composition and the forming method are not particularly limited.

Examples of the forming method include a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermochemical vapor deposition method, and the like. And a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a photochemical vapor deposition method can be mentioned.
When forming the vapor deposition film, the surface to be vaporized can be pretreated as needed. Specifically, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow, etc. Physical treatment such as electric discharge treatment or chemical treatment such as oxidation treatment using chemicals may be performed.

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

[Dry lamination adhesive layer 2 (E)]
The dry lamination adhesive layer 2 (E) is a layer that imparts interlayer adhesiveness in the laminated body, is a dry lamination adhesive layer adjacent to the sealant layer (F), and has the sealant layer (F) in the laminated body. It is a layer that plays a role of adhering to.
It is also possible to use an adhesive having the same composition as the dry lamination adhesive layer 2 (E) for a layer not adjacent to the sealant layer (F), but in that case, the dry lamination adhesive layer 1 (C). are categorized.
By having the above structure, good adhesiveness is obtained in the laminated body.

The amount of the dry lamination adhesive layer 2 (E) applied is preferably 0.5 g / m ² or more and 6 g / m ² 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 or the like are likely to occur in the dry lamination adhesive layer 2 (E). , Adhesiveness tends to decrease.

The dry lamination adhesive layer 2 (E) is preferably a layer formed from an aqueous dispersion in which an 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 then drying at 80 to 120 ° C. or melt-extruding 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 normal urethane-based anchor coating agent is used, and interlayer adhesion by the contents is improved. It is possible to prevent a decrease in strength, reduce delamination, and prevent a decrease in bag drop strength.

The content of the unsaturated carboxylic acid-modified polyolefin resin in the aqueous dispersion is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, further preferably 5 to 50% by mass, and 10 to 45% by mass. Is particularly preferable. By setting the content in the above range, good film forming property can be obtained.
Here, it is preferable that the aqueous dispersion does not substantially contain the non-volatile aqueous auxiliary. As a result, 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.
"Substantially free of the non-volatile water-based auxiliary agent" means that the non-volatile water-based auxiliary agent is not positively added to the system, and as a result, these are not contained. It is particularly preferable that the content of such a non-volatile aqueous aid is zero, but the content is, for example, less than 0.1% by mass with respect to the unsaturated carboxylic acid-modified polyolefin resin component as long as the effect of the present invention is not impaired. It does not matter if it is included to some extent.

The main solvent of the aqueous dispersion is water, but water-soluble alcohols, ethers and the like may be contained, and even if a small amount of organic solvent component added as a plasticizer or the like is contained in the resin component. good.
Further, if it is a volatile aqueous aid, a small amount may be contained. For example, an unsaturated carboxylic acid-modified polyolefin-based resin dispersed by containing a basic compound such as ammonia or a volatile organic amine compound. Stability can be imparted by preventing the aggregation of fine particles.
Further, by using the aqueous dispersion, the amount of harmful organic solvent discharged during the production of the laminate can be reduced, so that the adverse effect on the environment can be reduced.

Further, the unsaturated carboxylic acid-modified polyolefin resin is dispersed in the aqueous dispersion in the state of fine particles, and the number average particle diameter of the fine particles is preferably 1 μm or less, preferably 0.01 μm or more and 1 μm. The following is more preferable. Further, the weight average particle diameter is preferably 1 μm or less, more preferably 0.01 μm or more and 1 μm or less. If it is smaller than the above range, it becomes difficult to prepare an aqueous dispersion and the cost tends to increase because the process is complicated. If it is larger than the above range, the dry lamination adhesive layer 2 (E) ) Is likely to be inhomogeneous, which may reduce the adhesiveness.

(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 from 120,000 to 120,000, particularly preferably from 30,000 to 100,000, and most preferably from 35,000 to 80,000.
If the weight average molecular weight is less than the above range, the adhesiveness to the substrate tends to be lowered, and the obtained coating film tends to be hard and brittle. On the other hand, if the weight average molecular weight exceeds the above range, the resin It tends to be difficult to make it water-based.

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

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

Examples of the acid ester include methyl ester, ethyl ester, propyl ester, dimethylaminoethyl ester and the like.
The polyolefin-based resin is a homopolymer or a copolymer using one kind or two or more kinds of α-olefins as a raw material monomer.
Specific examples of the α-olefin include 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.

Further, the polyolefin may be a copolymer in which a monomer other than α-olefin is used in combination as the monomer. Examples of such other monomers include vinyl ester-based monomers such as vinyl acetate.

Specific examples of the polyolefin-based 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, and the like. Polyethylene-based resins such as low-density polyethylene (LDPE) and ionomer; polypropylene-based resins; polybutadiene-based resins, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers; unsaturated carboxylic acid-modified polyolefin-based resins, etc. Be done.

The unsaturated carboxylic acid-modified polyolefin resin has a structure derived from an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride in 0.01% by mass or more and 5% by mass or less in a completely unsaturated carboxylic acid-modified polyolefin resin. It is preferable that it is contained in the ratio of. If it is less than the above range, it tends to be difficult to make the resin water-based (liquefaction), and it tends to be difficult to obtain a good aqueous dispersion. If it is more than the above range, the stability of the aqueous dispersion is lowered, and it tends to be difficult to adjust the number average particle size of the unsaturated carboxylic acid-modified polyolefin resin in the aqueous dispersion within the above range, and adhesion is likely to occur. There is a risk of reducing the sex.

(Non-volatile water-based aid)
In the present invention, the non-volatile aqueous auxiliary is a non-volatile agent or compound added for the purpose of promoting aqueous dispersion or stabilizing the aqueous dispersion in the production of the aqueous dispersion.
Here, the non-volatile means that it does not have a boiling point at normal pressure or has a high boiling point at normal pressure (for example, 300 ° C. or higher).

Examples of the non-volatile aqueous aid include compounds having a protective colloidal action such as emulsifiers and surfactants, modified waxes, acid-modified compounds having a high acid value, and water-soluble polymers.
Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier, which are generally used for emulsion polymerization and also include surfactants. For example, examples of the anionic emulsifier include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, and vinyl sulfosuccinates. Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, and ethylene oxide-propylene oxide. Examples thereof include compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid ester, and examples of the amphoteric emulsifier include laurylbetaine and lauryldimethylamine oxide.

Compounds having a protective colloidal action such as surfactants, modified waxes, acid-modified compounds having a high acid value, and as water-soluble polymers, polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, Acid-modified polyolefin waxes having a number average molecular weight of 5000 or less, such as modified starch, polyvinylpyrrolidone, polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, and carboxyl group-containing polyethylene-propylene wax, and their respective Salt, acrylic acid-maleic anhydride copolymer and its salts, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating polymer, (meth) A carboxyl group-containing polymer having an unsaturated carboxylic acid content of 10% by mass or more, such as an acrylic acid- (meth) acrylic acid ester copolymer and a salt thereof, polyitaconic acid and a salt thereof, and a water-soluble acrylic common weight having an amino group. Examples thereof include compounds generally used as dispersion stabilizers for fine particles, such as coalescing, gelatin, gum arabic, and casein.

[Sealant layer (F)]
The sealant layer (F) is a layer that imparts functions such as heat sealability, bending resistance, and impact resistance to the laminated body, and is adjacent to the dry lamination adhesive layer 2 (E) in the laminated body. , It is a layer laminated on the outermost layer of the laminated body.
The sealant layer (F) may be one layer or may be composed of two or more layers. In the case of two or more layers, it may be a layer having the same composition or a layer having a different composition. However, the layer constituting the surface layer of the laminated body preferably contains a resin having excellent heat-sealing properties.

Specific resins include, for example, polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, metallocene polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, and the like. Ethylene- (meth) ethyl acrylate copolymer, ethylene- (meth) acrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene and other polyolefin resins are made into acrylic acid, methacrylic acid, and anhydrous. Polypropylene-based resin modified with unsaturated carboxylic acid such as maleic acid, fumaric acid and others, ternary copolymer resin of ethylene- (meth) acrylic acid ester-unsaturated carboxylic acid, cyclic polyolefin resin, cyclic olefin copolymer, polyethylene terephthalate. (PET), polyacrylonitrile (PAN) and the like.

As the sealant layer (F), a resin film or sheet using one or more of the above resins, a resin coating film, or the like can be used.
If necessary, a known bending resistance improving agent, an inorganic or organic additive, or the like can be added to the above resin.
As the film or sheet forming the resin layer, any unstretched film or sheet, or a stretched film or sheet stretched in the uniaxial or biaxial direction can be used.

Among the above, the sealant layer (F) preferably contains a polyolefin resin, more preferably LDPE or LLDPE, and particularly preferably LLDPE, from the viewpoint of heat sealability and content resistance.
As a method of laminating the sealant layer (F), a method of extruding and 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 like. Examples thereof include a method of thermocompression bonding the sheet, and a method of thermocompression bonding the resin film for the sealant layer (F) or the sheet is preferable.

The thermocompression bonding is preferably performed by a pressurizing device heated to 80 ° C. or higher and 200 ° C. or lower. When the temperature is lower than the above range, the effect of thermocompression bonding tends to be difficult to be fully exhibited, and when the temperature is higher than the above range, various changes due to thermocompression bonding tend to proceed rapidly, which complicates control. It tends to be inferior in productivity.

By laminating the sealant layer (F) according to the above method, the lamination strength at the interface of each layer in the high content resistance high drop bag strength laminate, particularly the laminating strength of the sealant layer (F), of the layer laminated by the extrusion laminating Even at the interface, it is improved, and in particular, the laminating strength of the interface of the dry lamination adhesive layer 2 (E) is improved, and the packaging bag can sufficiently withstand even a heavy content.

Further, not only the laminating strength is improved, but also the contents of the packaging bag are alcohol-containing substances, acidic substances, and alkaline substances, and even when the contents are stored for a long time in a filled state, it is sufficient. It is possible to maintain a high laminating strength, and the content resistance of the packaging bag is improved.
Further, by improving the laminating strength, the drop impact resistance of the packing bag filling is improved.
Further, this makes it possible to prevent the sealant layer (F) from being peeled off at the time of hand-cutting and opening after long-term storage, thereby preventing the hand-cutting and opening property from being lowered.

The thickness of the sealant layer (F) is preferably 5 to 500 μm, more preferably 10 to 250 μm, and even more preferably 15 to 100 μm. If it is thinner than the above range, it tends to be difficult to obtain sufficient heat seal strength, and if it is thicker than the above range, the cost tends to increase and the film tends to become hard and workability tends to deteriorate.

<Content resistance>
The content resistance in the present invention includes, for example, weight resistance, acid resistance, alkali resistance, alcohol resistance, surfactant resistance, spice resistance, oil resistance, organic solvent resistance, chemical resistance 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 medicinal ingredient (limonen, menthol, etc.) content It shows that the laminate, the packaging material, and the packaging have resistance to the contents of.

The laminate, packaging material, and packaging bag according to the present invention have one or more of the above-mentioned group of various content-resistant properties.
If the content resistance is insufficient, the laminate, the packaging material, and the packaging will cause delamination or breakage, or poor manual cutting and opening.

<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 high-drop bag strength packaging bag of the present invention can be manufactured by heat-sealing the above-mentioned content-resistant high-drop bag strength packaging material into a bag shape.

The aspect of the packaging bag according to the present invention is not particularly limited, and for example, a flat bag such as a three-way seal type bag or a four-way seal type bag, a pillow type bag, a self-standing bag such as a standing pouch, or a gusset bag. Alternatively, it may be a packaging bag of any aspect such as these application forms.

The raw materials used in the examples are as follows.
PET film 1: Biaxially stretched PET film manufactured by Toyobo Co., Ltd., T-4102. Single-sided corona treatment. 12 μm thick.
PET film 2: A biaxially stretched PET film with a single-sided aluminum vapor-deposited film manufactured by Toray Film Processing Co., Ltd. 12 μm thick. Aluminum film thickness 40 nm.
PBT film 1: Biaxially stretched PBT film manufactured by Kohjin Film & Chemicals Co., Ltd., Boblet ST. Single-sided corona treatment. 15 μm thick.
Nylon film 1: Biaxially stretched nylon film manufactured by Toyobo Co., Ltd., Harden film N1200. Double-sided corona treatment. Thickness 15 μm.
Nylon film 2: Biaxially stretched nylon film manufactured by Toyobo Co., Ltd., Harden film N7476. 15 μm thickness. Single-sided aluminum vapor deposition.
Polyethylene resin 1: Linear low density polyethylene manufactured by Prime Polymer Co., Ltd., SP1
071C. MFR 10g / 10 minutes.
LLDPE film 1: Mitsui Chemicals Tohcello Co., Ltd. T.I. U. X-HC. 100 μm thick.
Aluminum foil 1: Toyo Aluminum Co., Ltd. 1N30.7 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 Ltd. An 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). Further, 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, the DL adhesive 2 as the 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 a laminate A.

Next, the LLDPE film 1 as the sealant layer (F) was superposed on the two DL adhesive surfaces of the laminated body A and thermocompression bonded at 100 ° C. with a laminated nip roller to obtain a laminated body.

Layer structure 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 carried out using the obtained laminate. The results are shown in Table 1.

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

[Example 3]
A laminate was obtained by the same operation as in Example 1 except that the thermocompression bonding temperature 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). Further, 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, the DL adhesive 2 as the 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 the mixture was dried.
Next, the PET film 1 as the reinforcing layer (B) was superposed on the two DL adhesive surfaces and thermocompression bonded at 120 ° C. with a laminate nip roller to obtain a laminated body A.

Layer structure 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 DL adhesive 2 as the dry lamination adhesive layer 2 (E) on one surface of the PET film as the reinforcing layer (B) of the obtained laminate A is 3 g / m ² after drying. Was applied and dried, and then the LLDPE film 1 as a sealant layer (F) was laminated on the two DL adhesive surfaces and thermocompression bonded at 120 ° C. with a laminate nip roller to obtain a laminate.

Layer structure 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)
The obtained laminate was used and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 5]
A PET film 2 including an aluminum vapor-deposited film as a base material layer (A) and a nylon film 1 as a reinforcing layer (B) are dried via a DL adhesive 1 as a dry lamination adhesive layer 1 (C). The film was laminated by lamination, and further, DL adhesive 2 as the dry lamination adhesive layer 2 (E) was applied to the surface of the nylon film in an amount such that the weight after drying was 3 g / m ² , and the film was dried. Next, the LLDPE film 1 as the sealant layer (F) was superposed on the two DL adhesive surfaces and thermocompression bonded at 120 ° C. with a laminate nip roller to obtain a laminate.

Layer structure of laminate: PET film 2 (12 μm) / aluminum vapor-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)
The obtained laminate was used and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Examples 6 and 7]
The operation was carried out in the same manner as in Example 2 except that the coating amount of the dry lamination adhesive layer 2 (E) was changed to the coating amount shown in Table 1, and a laminated body was obtained and evaluated in the same manner. The results are shown in Table 1.

[Example 8]
The PET film 1 as the base material layer (A) was changed to the PBT film 1, and the reinforcing layer (B) and the dry lamination adhesive layer (C) for laminating the reinforcing layer (B) were not provided. Except for the above, the same operation as in Example 2 was carried out to obtain a laminated body, which was evaluated in the same manner. 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 the DL adhesive 2 was changed to the DL adhesive 1. The results are shown in Table 1.
<Evaluation method>

[Laminate strength]
A strip-shaped test piece having a width of 15 mm was cut out from the laminate, and approximately 10 mm at the end short side of the test piece was peeled off with an adhesive layer adjacent to the sealant layer (F) sandwiched between them. Using RTC-1310A manufactured by Orientec, the maximum load when peeled by the T-shaped peeling method (tensile speed 50 mm / min) under an atmosphere of 25 ° C. was measured and used as the laminating strength (N / 15 mm width). Furthermore, the peeling interface site was confirmed. The notations in Table 1 have the following meanings. Laminate strength of 3N / 15mm or more was accepted.
In the table, "non-peeling" indicates that the laminate strength was too strong to be peeled, and "already peeled" indicates that the laminate had already been peeled before the peeling test.

[Content resistance]
A bag was prepared by heat-sealing three sides of the laminate, and the contents were filled and sealed, and then stored at 40 ° C. for 7 days for 1 month, and the content resistance was evaluated by the decrease in the laminate strength.

[Drop impact resistance]
Using the laminate, the gusset bag shown in FIG. 2 was prepared with the following dimensions, filled with 500 ml of water, degassed and sealed, and sealed to prepare a test piece.
Then, after storing at 3 ° C. for 24 hours, the test piece was dropped 10 times from a height of 1.2 m in a horizontal orientation, and then dropped 10 times in a vertically standing orientation to check for water leakage. Detected a defect.
Overall width of the bag: 135mm
Overall length of bag: 225 mm
Folded length of bottom gusset 14: 37 mm
Width of the maximum part of the spout part seal part 17: 40 mm
Length of maximum part of spout part seal part 17: 55 mm
Overall width of the position where the half-cut line 21 is provided: 24 mm
Tapered angle of spout 20: Approximately 36 °
Method of manufacturing half-cut wire 21: Laser irradiation Half-cut wire spacing: 0.7 mm
Half-cut line depth: Approximately 30 μm

[Summary of evaluation results]
The laminates of Examples 1 to 8 of the present invention showed strong laminate strength and content resistance, and the packaging bag made from the laminate showed 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 material layer (A)
3 Dry lamination adhesive layer 1 (C)
4 Reinforcing layer (B)
5 Barrier layer containing metal element (D)
6 Dry lamination adhesive layer 2 (E)
8 Sealant layer (F)
10 Gazette bag 11, 11'Wall surface film 12 Bottom film folded part 13a, 13b Bottom film notch part 14 Gusset part 15 Bottom seal part 16a, 16b Side seal part 17 Note outlet part Seal part 18 Top seal part 19a, 19b Cut Notch 20 Spout 21 Half-cut line 22 Notch

Claims (8)

At least, it contains a base material 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). It is a laminated body with high content resistance and high drop bag strength.
The base material layer (A), the dry lamination adhesive layer 1 (C), the metal element-containing barrier layer (D), and the dry lamination adhesive layer 2 (E) are laminated in this order.
The dry lamination adhesive layer 2 (E) is a layer formed from an aqueous dispersion in which an unsaturated carboxylic acid-modified polyolefin resin is dispersed, and is adjacent to the sealant layer (F).
The coating amount of the dry lamination adhesive layer 2 (E) is 0.5 g / m ² or more and 6 g / m ² or less, and contains LDPE or LLDPE.
The sealant layer (F) contains LDPE or LLDPE, and the thickness of the sealant layer (F) is 10 to 250 μm.
The sealant layer (F) is a layer formed by laminating films by a pressurizing device heated to 80 ° C. or higher and 200 ° C. or lower.
A gusset bag having the following dimensions shown in FIG. 2 produced using the laminate was filled with 500 ml of water, degassed and sealed, and the sealed test piece was stored at 3 ° C. for 24 hours and then stored at a height of 1.2 m. If the test piece is dropped 10 times in a horizontal orientation and then 10 times in a vertically upright orientation, no water leakage will occur.
Content resistance High drop bag strength laminated body.
Overall width of the bag: 135mm
Overall length of bag: 225 mm
Folding length of the bottom gusset: 37mm
Width of the maximum part of the spout part seal part: 40 mm
Maximum length of the spout part seal part: 55 mm
Overall width at the position where the half-cut line is provided: 24 mm
Tapered angle of spout: Approximately 36 °
How to make half-cut wire: Laser irradiation
Half-cut line spacing: 0.7mm
Half-cut line depth: Approximately 30 μm The high-strength laminated body having a high content resistance and a bag drop, according to claim 1, further comprising a reinforcing layer (B). The aqueous dispersion is substantially free of the non-volatile aqueous aid.
The number average particle size of the unsaturated carboxylic acid-modified polyolefin resin in the aqueous dispersion is 1 μm or less.
The high-strength laminate with high content resistance according to claim 1 or 2. The unsaturated carboxylic acid-modified polyolefin resin has a structure derived from unsaturated carboxylic acid or unsaturated carbonic anhydride in a total unsaturated carboxylic acid-modified polyolefin resin in an amount of 0.01% by mass or more and 5% by mass. The high content resistance high drop bag strength laminate according to claim 3, which contains a ratio of% or less. Any one of claims 1 to 4, wherein 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. The high-thickness laminated body with high content resistance and high drop bag described in item 1. 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, and chemical resistance component resistance. The high content resistance high drop bag strength laminate according to any one of claims 1 to 5, which is one type or two or more types. A packaging material having a high content-resistant high-drop bag strength according to any one of claims 1 to 6, comprising the high-content- resistant high-drop bag strength laminate . A high-strength packaging bag with high physical characteristics, which is made from the high- strength packaging material with high physical characteristics according to claim 7.

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