JP6589292B2 - Agricultural packaging materials - Google Patents

Description

  Since the present invention has high resistance to organic phosphorus / organic sulfur-based agricultural chemicals containing various organic compounds such as glyphosate, fenitrothion, malathion, and alcohols contained in agricultural chemicals, it has high interlayer adhesion strength. The present invention relates to an excellent packaging material that has a sealant layer that is retained for a long time and has excellent sealant properties, and a packaging container using the packaging material, that is, a packaging material for agricultural chemicals.

Conventionally, as a packaging bag for sealing and packaging liquid detergents, shampoos, rinses, etc., for example, a packaging bag produced by sealing a laminate in which a base material layer, a barrier layer, a sealant layer, etc. are laminated via an adhesive layer, respectively. Was used.
However, if the packaged content is a highly permeable liquid such as an agrochemical, these components will penetrate the laminate during long-term storage, especially the adhesive layer between the barrier and sealant layers. As a result, there was a problem that the sealant layer peeled off from the barrier layer and the packaging bag was damaged.

  As a method of laminating a sealant layer on the barrier layer, generally, an anchor coat layer is provided as an adhesive layer on the barrier layer surface, and a resin of the sealant layer is extruded thereon to laminate as a coat, or a film is previously formed on the barrier layer surface. A method is used in which the film of the sealant layer formed above is laminated by a dry laminating method using a dry laminating adhesive such as a two-component curable polyurethane adhesive.

As an anchor coat agent (AC agent) used for the anchor coat layer, AC agents such as an organic titanium AC agent and a polybutadiene AC agent are commercially available.
However, when the contents are all agricultural chemicals, the content resistance is insufficient, and as a test for the storage stability of the packaging material in which the contents are hermetically sealed, for example, an accelerated test, the temperature is 60 ° C. When a storage test of about a week was performed, there was a problem that the barrier layer peeled off from the sealant layer.

  That is, contents containing organic compounds, such as organophosphorus / organic sulfur pesticides containing various organic compounds such as glyphosate, fenitrothion, malathion, alcohols, permeate the sealant layer of the packaging container during storage, and It has been known that an adhesive layer made of various dry laminating adhesives and adhesive resins is eroded to cause delamination between the base film and the sealant film.

Similarly, when the sealant layer is bonded to the barrier layer by the dry laminating method, similarly, the content resistance of the adhesive for dry laminating is insufficient, and the sealant layer peels from the barrier layer according to the storage test. There was a problem.
As techniques related to these, the following are known.
For example, a film laminated with a polyurethane adhesive layer containing a urea bond and a sealant film accommodates a liquid containing a strongly permeable substance, an acidic substance, an alkaline substance, a fragrance, an oil, a surfactant, and a high boiling point organic solvent. Packaging bags are known.

  That is, the invention relates to an ink bag for an ink jet device, a flexible packaging bag for food, detergent, household goods, health and medical related products, etc., and the contents to be stored are liquid, and alcohols, bath agents Even if it contains a strong permeable substance containing volatile components with strong penetrating power, such as sachets and poultices, and fragrances, vinegar, oil, alkaline substances, etc. The purpose of the present invention is to provide a flexible packaging bag for liquids that does not cause delamination and has excellent storage stability without reducing the adhesive strength of the agent layer. It is known that a flexible packaging bag for liquid is obtained by a laminated film obtained by laminating a sealant film made of a polyethylene film through a polyurethane adhesive layer containing a urea bond. Are (see Patent Document 1).

In addition, the anchor coat layer is a laminate composed of an anchor coat agent containing 85% by weight or more of a compound having two or more isocyanate groups, so that the laminate strength of the contents does not decrease even when a fragrance is filled. The body is known.
That is, it is a laminate having an aluminum foil layer excellent in gas barrier properties and the like, and particularly used as various packaging materials, volatiles such as fragrances, poultices, bathing agents and the like, and organic solvents such as alcohol. Providing a laminate that maintains the original excellent laminate strength and prevents the laminate strength from falling between layers even if a highly permeable material containing materials, surfactants, acidic substances, alkaline substances, etc. is packaged. Therefore, at least one surface of the aluminum foil layer is formed with a hydrothermal modification layer by hydrothermal modification treatment, and an anchor coat layer and an adhesive resin are formed on the hydrothermal modification layer. A layer, an anchor coat layer, and a plastic substrate layer are laminated at least in this relative order, and the anchor coat layer has two or more isocyanate groups. That the compound was composed of an anchor coating agent containing more than 85% by weight to form a laminate invention are known (see Patent Document 2).

Further, in a laminate for a container in which a sealant resin layer is laminated on at least the content side of the base material sheet, the silicon oxide is directly bonded to the base material sheet side of the innermost sealant resin layer on the content side. A container laminate having a vapor deposition layer is known.
However, even in these techniques, the alcohol resistance, non-adsorption property, and sealant property are not satisfactory.

JP 2013-95454 A JP 2009-172824 A

  The present invention solves the above-mentioned problems, and is effective for organic phosphorus / organic sulfur-based agricultural chemicals containing various organic compounds such as glyphosate, fenitrothion, malathion, alcohols, etc. It is an object to provide a packaging material for agricultural chemicals having excellent adsorptivity and excellent sealant properties.

  Agrochemicals may use active ingredients such as N-phenyltetrahydrophthalimide compounds as they are, but usually, the active ingredients are mixed with various carriers such as liquid carriers, and surfactants, dispersants, It is formulated into various preparation forms by adding a fixing agent, a stabilizer, and other preparation adjuvants.

Examples of the liquid carrier include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic carbonization, etc. Hydrogen (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides ( N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil, etc. are used.
As the gaseous carrier, for example, chlorofluorocarbon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas or the like is used.

  Examples of the surfactant include alkyl sulfate ester salts, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, etc. Is used.

  Furthermore, as the stabilizer, for example, PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol and 3-tert- A mixture with butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like.

Therefore, when these are filled in a conventional packaging container made of a flexible laminate, the concentration of active ingredients, etc. changes, and the laminate is likely to delaminate so that it can be stored stably for a long period of time. There wasn't.
However, these problems are solved by filling the packaging container comprising the laminate of the present invention. Furthermore, since the packaging container which consists of a laminated body of this invention does not have a problem that a low molecular weight substance elutes into the contents from the inside of a laminated body, it can be preferably used for packaging of various agricultural chemicals.

  As a result of various studies, the inventor has at least a polyester-based resin film layer, an anchor coat layer laminated adjacently on the polyester-based resin film layer, and laminated adjacently on the anchor coat layer. A packaging material for agricultural chemicals having a polyolefin-based resin layer, wherein the anchor coat layer is formed from a polyester-based specific aqueous dispersion containing a polyolefin copolymer resin containing an unsaturated carboxylic acid or an anhydride thereof and a crosslinking agent. It has been found that a packaging material or the like, which is a layer formed by applying and drying on a resin film layer, achieves the above object.

The present invention is characterized by the following points.
1. Agrochemical packaging having at least a polyester resin film layer, an anchor coat layer laminated adjacently on the polyester resin film layer, and a polyolefin resin layer laminated adjacently on the anchor coat layer The anchor coat layer includes a polyolefin copolymer resin containing 0.01 to 5% by mass of an unsaturated carboxylic acid or an anhydride thereof and a cross-linking agent, but does not include a non-volatile aqueous agent. An aqueous dispersion obtained by dispersing the polyolefin copolymer resin in an aqueous solvent so that the number average particle diameter thereof is 1 μm or less is applied onto the polyester resin film layer and dried. A packaging material for agricultural chemicals as described above.
2. 2. The packaging material for agricultural chemicals according to 1 above, wherein in the aqueous dispersion, the mass ratio of the polyolefin copolymer resin and the crosslinking agent is 1: 1 to 10: 1.
3. The packaging material for agricultural chemicals according to 1 or 2 above, wherein the anchor coat layer has a dry thickness of 0.1 to 2 µm.
4). 4. The packaging material for agricultural chemicals according to any one of the above 1 to 3, further comprising a polyolefin resin film layer on a surface of the polyolefin resin layer opposite to the surface adjacent to the anchor coat layer.
5. The packaging material for agricultural chemicals according to 4 above, further comprising a barrier layer on the surface of the polyester resin film layer opposite to the anchor coating layer lamination surface.
6). 4. The method for producing a packaging material for agricultural chemicals according to any one of 1 to 3, wherein the polyolefin resin layer is formed by extruding a polyolefin resin on the anchor coat layer at a temperature of 300 ° C. or higher. The above manufacturing method.
7). 6. The method for producing a packaging material for agricultural chemicals according to 4 or 5 above, wherein the polyolefin-based material is formed by extrusion-coating a polyolefin-based resin at a temperature of 300 ° C. or higher (300 to 340 ° C.) on the anchor coat layer. The said manufacturing method of laminating | stacking the said polyolefin resin film layer by a sandwich lamination method through a resin layer.
8). A packaging container obtained by superposing the packaging material for agricultural chemicals according to any one of the above 1 to 5 so that the polyolefin resin layer or the polyolefin resin film layer is the innermost layer and sealing the end thereof.
9. 9. The interlayer adhesive strength between the polyester-based resin film layer and the polyolefin-based resin layer after filling with agricultural chemicals and storing for 30 days under dry conditions at 60 ° C. is 4 N / 15 mm width or more. Packaging container.
10. 10. The packaging container according to 8 or 9 above, which is a packaging container for agricultural chemicals.

  As described above, the present invention is, for example, formed by sealing a laminate for agricultural chemicals in which a base material layer, an anchor coat layer, and a polyolefin resin layer are laminated in this order, and the anchor coat layer is unsaturated. An aqueous solution comprising a polyolefin copolymer resin containing a carboxylic acid or anhydride thereof in the range of 0.01 to 5% by mass and a crosslinking agent, and the polyolefin copolymer resin dispersed so that the number average particle diameter thereof is 1 μm or less. It is formed using a dispersion.

  And it forms so that the non-volatile aqueous | water-based auxiliary | assistant auxiliary agent may not be included substantially in the aqueous dispersion, Desirably, it apply | coats and heat-drys so that the thickness at the time of drying may become 0.1-2 micrometers. Further, the crosslinking agent contained in the anchor coating agent is an invention characterized in that crosslinking is completed by extrusion coating of a polyolefin resin at 300 ° C. or higher.

  The polyolefin resin layer is formed by a method of extruding and coating a polyolefin resin on the surface of the anchor coat layer or a method of extruding and laminating a polyolefin resin film using a similar polyolefin resin. A packaging bag for agricultural chemicals.

  The anchor coat layer of the packaging material for agricultural chemicals of the present invention contains a polyolefin copolymer resin containing 0.01 to 5% by mass of an unsaturated carboxylic acid or its anhydride and a crosslinking agent as described above. A polyester-based resin film, which is a base material, is an aqueous dispersion that does not contain an agent, and is obtained by dispersing the polyolefin copolymer resin in an aqueous solvent so that the number average particle diameter thereof is 1 μm or less. It is a layer formed by applying onto a layer, drying and curing.

Therefore, the resistance to the organic compound contained in the agricultural chemical is improved, and stable laminate strength and sealing strength can be maintained even if the contents of the agricultural chemical are stored for a long time.
Moreover, according to the manufacturing method of this invention, the packaging material for agricultural chemicals which is excellent also in heat fusion property with agrochemical resistance and non-adsorption property can be manufactured easily.

It is a schematic sectional drawing which shows an example about the layer structure of the packaging material for agricultural chemicals of this invention. It is a schematic sectional drawing which shows another example about the layer structure of the packaging material for agricultural chemicals of this invention. It is a schematic sectional drawing which shows another example about the layer structure of the packaging material for agricultural chemicals of this invention.

(1) Structure of packaging material for agricultural chemicals The basic structure of the packaging material for agricultural chemicals of the present invention includes a specific base material layer (1), an anchor coat layer (2) in which a specific aqueous dispersion is cured, and a specific sealant layer. (3) is laminated. This aspect is shown in the cross-sectional view of FIG.
In the present invention, if the base material layer (1), the anchor coat layer (2), and the sealant layer (3) are basically laminated in this order from the outer layer to the inner layer, other layers are added. You may laminate.

For example, you may have a polyolefin-type resin film layer (4) on the surface of a sealant layer. An example of this aspect is shown in the cross-sectional view of FIG.
The base material layer of the present invention may be composed of multiple layers, and the adhesive layer of each layer may be composed of an adhesive film.

Further, a barrier layer (5) may be further formed on the surface of the polyester-based resin film layer, which is the base material layer, on the side opposite to the anchor coat layer laminating surface, to provide a packaging material for agricultural chemicals. An example of this aspect is shown in the cross-sectional view of FIG.
Next, each layer which comprises the packaging material for agricultural chemicals of this invention is demonstrated concretely.

(2) Base material layer The base material layer constituting the packaging material for agricultural chemicals of the present invention may be any material as long as the strength as a packaging material can be ensured, and is excellent in chemical or physical strength. An organic material such as a metal, an inorganic material such as a metal oxide, a metal oxide, or an organic material that can withstand the conditions of forming the film and the like, and can be satisfactorily maintained without impairing the properties of the deposited film of the inorganic oxide, for example, a film or Can be used as a sheet.

  Specifically, as such a film or sheet, polyolefin resin such as paper, aluminum foil, polyethylene resin or polypropylene resin, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density Polyethylene, stretched polypropylene, K-coated stretched polypropylene, cyclic polyolefin-based resin, K-coated stretched nylon, polyvinyl alcohol, polyacrylonitrile, ethylene-vinyl acetate copolymer resin, ionomer resin, ethylene- (meth) acrylic acid copolymer resin, Ethylene- (meth) acrylate copolymer resin, ethylene-propylene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, methylpentene resin, polybutene resin, acid-modified poly Refin resins, various polyamide resins such as nylon, polystyrene resins, low crystalline saturated polyesters or amorphous polyester resins, for example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyvinyl chloride, polychlorinated Vinylidene, polyvinylidene fluoride, ethylene tetrafluoroethylene resin, polyethylene tetrafluoroethylene resin, polycarbonate resin, polyurethane resin, acetal resin, cellulose resin, and the like can be used.

  In the present invention, among the above resins, it is preferable to use a film or sheet of polyester resin, polyolefin resin, or polyamide resin, and it is particularly preferable to use stretched polyethylene terephthalate. The polyester resin film or sheet such as stretched polyethylene terephthalate can also be used as a polyester resin film in other layers in the present invention.

  As the base material layer of the present invention, a polyester resin film is particularly desirable from the viewpoints of adhesion to the anchor coat layer, strength, processability, suitability as an agricultural chemical-resistant packaging material, and the like. For example, a film of polyester resin such as polyethylene terephthalate film or polyethylene naphthalate film obtained by polycondensation reaction of dicarboxylic acids such as terephthalic acid or derivatives thereof, 2,6-naphthalenedicarboxylic acid or derivatives thereof and ethylene glycol It is most preferable to use a sheet.

Moreover, when using a paper base material, it is preferable that the tear strength by JISP8116 is 15-70 gf, Preferably it is 20-50 gf. As such a paper base material, pure white roll paper, coated paper, kraft paper or the like can be used.
The resin film or sheet may be formed by using the film forming method such as extrusion method, cast molding method, T-die method, cutting method, inflation method, etc. It is produced by a method of forming a multilayer co-extrusion film using the above-described various resins, a method of using two or more kinds of resins, mixing them before forming a film, and forming a film.

Furthermore, if necessary, it can be used as various resin films or sheets stretched uniaxially or biaxially using a tenter method or a tubular method.
In the present invention, the thickness of the base film is preferably from 0.1 to 300 μm, more preferably from 1 to 100 μm, from the viewpoints of moldability and transparency. The base material is preferably subjected to a treatment for improving wettability such as corona treatment, ozone treatment, or flame treatment on the adhesive layer side.

In addition, when using one or more of the above-described various resins and forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. From a very small amount to several tens of percent, it can be arbitrarily added depending on the purpose.
In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. In this case, a modifying resin or the like can also be used.

(3) Anchor coat layer In this invention, an anchor coat layer is for adhere | attaching firmly the base material which consists of a polyester-type resin film layer, and the sealant layer which consists of a polyolefin-type resin layer.

  The anchor coat layer of the present invention contains a polyolefin copolymer resin containing 0.01 to 5% by mass of an unsaturated carboxylic acid or an anhydride thereof and a crosslinking agent, but does not contain a non-volatile aqueous agent. An aqueous dispersion obtained by dispersing the polyolefin copolymer resin in an aqueous solvent so that the number average particle diameter thereof is 1 μm or less is 0.1 to 2 μm on the polyester resin film layer. It is a layer formed by applying and heating and drying.

The anchor coat layer contains a cross-linking agent, and melt-extruded polyethylene is applied to the anchor coat layer so that the cross-linking agent causes a cross-linking reaction and is cured.
The polyethylene to be melt extruded must be 290-330 ° C.
When the temperature is lower than 290 ° C., the crosslinking does not proceed and the content resistance is deteriorated. On the other hand, when the temperature is higher than 330 ° C., the polyethylene resin is decomposed and the extrusion becomes difficult and the physical properties are lowered.

  The anchor coat layer having crosslinkability acts between the base material made of a polyester resin film layer or the like and the sealant layer made of a polyolefin resin layer or the like so as to react and bond strongly with both layers. Therefore, the three layers can be firmly bonded.

In the present invention, the polyolefin copolymer resin is dispersed in an aqueous solvent so that the number average particle diameter thereof is 1 μm or less, so that the agricultural chemical resistance is improved and adhesion to the base material layer or the sealant layer is achieved. Even when the contents are stored for a long period of time, a stable laminate strength and seal strength can be maintained.
On the other hand, when particles having a number average particle diameter larger than 1 μm are used, the pesticide resistance is not improved because the adhesive strength is not sufficient.

  Furthermore, the reason why the polyolefin copolymer resin containing 0.01 to 5% by mass of unsaturated carboxylic acid or anhydride thereof is sufficient when the amount of unsaturated carboxylic acid is lower than 0.01% by mass with the substrate. Adhesive strength cannot be exhibited and adhesive strength is low, so that sufficient agricultural chemical resistance cannot be ensured. On the other hand, when the amount of unsaturated carboxylic acid is higher than 5% by mass, the adhesive strength is sufficiently exhibited, but compatibility with agricultural chemicals is increased, and sufficient alcohol resistance cannot be ensured.

  The polyolefin copolymer resin used for the anchor coat layer of the present invention is an acid-modified polyolefin resin. And as unsaturated carboxylic acid component, unsaturated carboxylic acid and its anhydride are mentioned, Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid In addition to crotonic acid, half esters and half amides of unsaturated dicarboxylic acids. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.

The anchor coat layer used in the present invention contains an unsaturated carboxylic acid or an anhydride thereof in the range of 0.01 to 5% by mass, and a number average particle size of 1 μm or less, for example, 50 to 200 nm polyolefin resin. An aqueous dispersion composed of particles and a cross-linking agent and substantially free of non-volatile aqueous additive such as an emulsifier is applied and dried.
The aqueous dispersion to be the anchor coat layer of the present invention contains a crosslinking agent, and it is an essential requirement that the anchor coat layer be crosslinked or at least partially crosslinked. Thereby, strong adhesion between layers having high agrochemical resistance becomes possible.

  The content of the crosslinking agent in the aqueous dispersion serving as the anchor coat layer is required to be 10 to 100 parts by mass and preferably 15 to 80 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin. . When the content of the crosslinking agent is less than 10 parts by mass, sufficient adhesion cannot be obtained, and when it exceeds 100 parts by mass, the adhesiveness and flexibility are deteriorated and the aqueous dispersion is stable. Sex worsens.

  In the present invention, examples of the crosslinking agent include a crosslinking agent having self-crosslinking property and a crosslinking agent having a plurality of functional groups that react with carboxyl groups in the molecule. Specific examples include isocyanate compounds, melanin compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, adipic acid dihydrazide compounds, among which oxazoline group-containing compounds, carbodiimide compounds, and isocyanate compounds are used. It is preferable.

  Examples of the oxazoline group-containing compound include an oxazoline compound containing 2-isopropenyl-2-oxazoline, and the carbodiimide compound has two or more carbodiimide groups in one molecule, and is water-soluble and / or water-dispersible. A polyfunctional carbodiimide resin is mentioned.

Moreover, as an isocyanate compound, the isocyanate compound which hexamethylene diisocyanate contains is mentioned as a preferable compound.
By adding an organic solvent when the acid-modified polyolefin resin is dispersed in an aqueous medium, the dispersion can be promoted and the dispersed particle size can be reduced. The amount of the organic solvent used is preferably 1 to 45% by mass in the aqueous medium.
The anchor coat layer of the present invention is excellent in adhesiveness with the base material layer and the heat seal layer by thinly coating so that the thickness when dried is 0.1 to 2 μm.

  The reason why the thickness of the anchor coat layer when dried is 0.1 to 2 μm is that when the thickness is less than 0.1 μm, sufficient adhesion strength with the melt-extruded polyethylene cannot be obtained. On the other hand, when the thickness is larger than 2 μm, the coating amount is equal to that of the adhesive for dry laminating, so that there is a problem that the cost is increased and it cannot be used for actual production.

  In addition, non-volatile aqueous additives such as emulsifiers remain in the coating film even after drying, and even if a small amount, it has a great effect on the adhesive interface and reduces adhesion and water resistance. In the coating layer, a nonvolatile aqueous auxiliary agent such as an emulsifier is not added for the purpose of promoting aqueous formation or stabilizing the aqueous dispersion in the production process of the aqueous dispersion. For this reason, delamination does not occur, and the adhesiveness with the barrier layer is excellent and the adhesiveness with the intermediate layer is also excellent.

The coating amount of the aqueous dispersion used to form the anchor coat layer, 0.1 g / m ² or less, more preferably 0.05 to 0.1 / m ^2. This is 1/10 or less compared to the amount of normal adhesive used, and the low molecular weight trace components contained in the aqueous dispersion hardly pass through the sealant layer, so that the aqueous dispersion The contained trace components do not leak into the contents, and the contents can be prevented from deteriorating.

(4) Sealant layer As the sealant layer, polyolefin-based resins having various sealant properties that can be melted by heat and fused to each other, and the like can be used.
The sealant layer of the present invention is a layer made of a heat-sealable resin that can be melted by heat and fused to each other. Furthermore, it is preferable to have a barrier property to the contents.

  Examples of the heat-sealable resin preferably used in the present invention include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-vinyl alcohol copolymer resin, Ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid ethyl copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene, etc. Polyolefin resins obtained by modifying polyolefin resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc., terpolymer resins of ethylene- (meth) acrylate-unsaturated carboxylic acids , Cyclic polyolefin resin, cyclic Les fins copolymers, polyethylene terephthalate (PET), it can include one or resin comprising more poly acrylonitrile (PAN).

  And even if these resin is single layer, or laminating | stacking these resins suitably, the sealant layer of this invention can be formed. Examples thereof include low density polyethylene / ethylene-vinyl alcohol copolymer resin / low density polyethylene, low density polyethylene / cyclic polyolefin resin / low density polyethylene, and the like.

A film or sheet made of these resins may be used, and the surface thereof may be subjected to corona treatment, flame treatment, ozone treatment or the like as desired.
Examples of the sealant layer include a low-density polyethylene film, preferably a film obtained by multilayer extrusion of an ethylene vinyl alcohol resin as a barrier resin together with a polyethylene resin, and a film obtained by extruding a cyclic polyolefin copolymer with a polyethylene resin. .

  The thickness of the heat-sealable resin layer is not particularly limited, but is preferably 5 to 500 μm, more preferably 10 to 250 μm. If the thickness is less than 5 μm, a sufficient laminate strength cannot be obtained even if heat sealing is performed, and it does not function as a packaging container. When it is thicker than 500 μm, the cost increases and the film becomes hard and workability deteriorates.

In the present invention, in particular, it is desirable to melt-extrude a polyolefin-based resin at a temperature of 300 ° C. or higher to provide the resin layer on the anchor coat layer, whereby the crosslinking agent in the anchor coat layer acts, Cross-linking of the anchor coat layer is completed.
In addition, the sealant layer of the present invention includes one or more additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antiblocking agent, a flame retardant, a crosslinking agent, and a colorant as appropriate. Two or more kinds may be added.

(5) Adhesive layer In the present invention, the adhesive resin layer provided between the anchor coat agent layer and the sealant layer is preferably one that can be extruded and is compatible with the sealant.
When the sealant layer is polyolefin, low density polyethylene, low density linear polyethylene, medium density polyethylene, high density polyethylene, ionomer resin, ethylene-methacrylate resin, ethylene-methacrylic acid resin, ethylene-maleic acid graft polymer, ethylene An acrylic ester-maleic terpolymer resin is preferred.

The MFR of the adhesive resin composition of the present invention is preferably 2 to 100 g / 10 minutes, more preferably 5 to 20 g / 10 minutes at 190 ° C. in relation to the other layers of the present invention.
Moreover, it is preferable that the thickness of the contact bonding layer which consists of adhesive resin compositions is 0.1-200 micrometers, More preferably, it is 1-100 micrometers.

When the film thickness is lower than the above range, it is difficult to extrude easily, and the adhesive force is not exhibited. When the film thickness is higher than the above range, problems such as adhesive strength are solved, but the cost increases due to excessive use of the resin.
The adhesive layer of the present invention is preferably low-density polyethylene from the viewpoints of extrusion suitability and adhesiveness.

(6) Barrier layer In the laminate of the present invention, as the barrier layer, any barrier film or barrier that has a gas barrier property that prevents permeation of oxygen gas, water vapor, and the like and that prevents permeation of agricultural chemical components in the contents. A film can be used.
Examples of such a barrier film or barrier film include a vapor-deposited film made of an inorganic substance or an inorganic oxide, a metal foil, a barrier resin film, and a vapor-deposited film provided with the vapor-deposited film on a resin film.

  Specifically, aluminum vapor deposition film, alumina vapor deposition film, silica vapor deposition film, aluminum foil, aluminum vapor deposition polyester resin film, aluminum vapor deposition polypropylene film, silica vapor deposition polyester resin film, silica vapor deposition polyamide resin film, alumina vapor deposition polyester system Examples of the barrier film or barrier film include a resin film, an ethylene-vinyl alcohol copolymer film, a polyvinylidene chloride film, a polyvinyl alcohol film, and an MXD6 film.

When providing a vapor deposition film as a barrier layer, it can provide directly on a base material layer, without passing through adhesive layers, such as an adhesive agent. If necessary, light blocking properties that prevent transmission of visible light, ultraviolet light, and the like can be imparted.
Moreover, you may have two or more barrier layers. When it has two or more barrier layers, each may have the same composition or a different composition.

  Usually, the thickness of a barrier film becomes like this. Preferably it is 0.01-500 micrometers, More preferably, it is the range of 1-300 micrometers. Further, the thickness of the deposited film is, for example, 10 to 2000 mm, and preferably selected and formed arbitrarily within the range of 10 to 1000 mm. Specifically, in the case of an aluminum deposited film, the film thickness is preferably 10 to 600 mm, and more preferably 10 to 400 mm. In the case of a silicon oxide or aluminum oxide deposited film, the film thickness is preferably 10 to 500 mm, more preferably 10 to 300 mm.

Moreover, you may perform the process which improves wettability, such as a corona process, an ozone process, and a flame | frame process, on the one or both surfaces of a barrier layer.
A conventionally known metal foil can be used as the metal foil made of an inorganic substance or an inorganic oxide. Aluminum foil or the like is preferable from the viewpoint of gas barrier properties that prevent the transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent the transmission of visible light, ultraviolet light, and the like.

A vapor deposition film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly limited.
As a method for forming a vapor deposition film, for example, 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, a plasma chemical vapor deposition method, a thermochemistry, or the like. Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

  Examples of the deposited film include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), Lead (Pb), zirconium (Zr), yttrium (Y) and other inorganic or inorganic oxide vapor deposition films can be used. In particular, an aluminum metal vapor-deposited film or a silicon oxide or aluminum oxide vapor-deposited film is preferably used as a packaging material.

The case where a silicon oxide vapor deposition film is provided as the vapor deposition film will be described in more detail.
The vapor-deposited film (thin film) of silicon oxide is represented by the general formula: SiO _x (wherein x represents a number from 0 to 2), and the value of x is preferably 1.3 to 1.9. The silicon oxide thin film may be mainly composed of silicon oxide, and may further contain at least one kind of compound composed of one kind of carbon, hydrogen, silicon or oxygen, or two or more kinds of elements by chemical bonding or the like.

For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. As content which said compound contains in the vapor deposition film | membrane of a silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%.

  Moreover, when a silicon oxide thin film contains the said compound, it is preferable that content of a compound is reducing toward the depth direction from the surface of the vapor deposition film | membrane of a silicon oxide. As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, the vapor deposition of the base material layer and the silicon oxide at the interface with the base material layer due to the low content of the above compound. The tight adhesion with the film becomes strong.

A gas barrier coating film may be further provided on the deposited film in order to improve the gas barrier property.
In the present invention, the gas barrier coating film is an alkoxide hydrolyzate obtained by polycondensation of an alkoxide and a water-soluble polymer by the sol-gel method in the presence of a sol-gel method catalyst, acid, water and an organic solvent. It is a film | membrane which consists of a hydrolysis condensate of an alkoxide. In some cases, the gas barrier composition may further contain a silane coupling agent.

Examples of the alkoxide that can be used in the gas barrier composition include a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an atomic valence of M), and preferably at least one alkoxide represented by Can be used. Here, as the metal atom M, silicon, zirconium, titanium, aluminum or the like can be used.

Specific examples of the organic group represented by R ¹ and R ² include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. Can be mentioned. In the same molecule, these alkyl groups may be the same or different. Examples of such alkoxides include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC _4). H ₉ ) _{4 and the} like.

As the water-soluble polymer that can be used in the gas barrier composition, either a polyvinyl alcohol-based resin or an ethylene / vinyl alcohol copolymer or both can be preferably used.
These resins may be commercially available. For example, as an ethylene / vinyl alcohol copolymer, Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 29 mol%) and the like can be used.

  Moreover, as polyvinyl alcohol, RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., Kuraray Poval LM-20SO (degree of saponification = 40%) manufactured by Kuraray Co., Ltd. Polymerization degree = 2,000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, degree of polymerization = 1,400) and the like can be used.

As the sol-gel catalyst, a tertiary amine that is substantially unnecessary in water and soluble in an organic solvent is used.
Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. In particular, N, N-dimethylbenzylamine is preferable, and for example, 0.01 to 1.0 part by mass, especially about 0.03 part by mass is used per 100 parts by mass of the total amount of alkoxysilane and silane coupling agent. It is preferable to do.

  Examples of the acid used in the gas barrier composition include mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, organic acids such as acetic acid and tartaric acid, and others. The amount of the acid used is preferably 0.001 to 0.05 mol, more preferably 0.01 to 0, based on the total molar amount of the alkoxide and the alkoxysilane component (for example, silicate moiety) of the silane coupling agent. 0.03 mole.

As the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.
As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used, and in particular, an organoalkoxysilane having an epoxy group is suitable, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or the like can be used. The above silane coupling agents may be used alone or in combination of two or more.

In this invention, the usage-amount of the above silane coupling agents can be used within the range of about 1-20 mass parts with respect to 100 mass parts of said alkoxides.
The content of the water-soluble polymer in the gas barrier composition is preferably in the range of 5 to 500 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. In the above, if it exceeds 500 parts by mass, the brittleness of the gas barrier coating film to be formed becomes large, and its weather resistance and the like are also unfavorable.

Specific examples of the method for forming the gas barrier coating film will be described below.
First, a gas barrier coating solution is prepared by mixing an alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, water, an organic solvent, and, if necessary, a silane coupling agent. To do. In the gas barrier coating liquid, the polycondensation reaction gradually proceeds.

  Next, the gas barrier coating solution is applied onto the deposited film by a conventional method and dried. By drying, the polycondensation of the alkoxide and vinyl alcohol polymer (and silane coupling agent) further proceeds to form a composite polymer layer. Preferably, a plurality of composite polymer layers can be laminated by repeating the above operation.

Finally, the laminate coated with the coating solution is heated at a temperature of 20 to 250 ° C., preferably 50 to 220 ° C., for 1 second to 10 minutes. Thereby, a gas barrier coating film can be formed on the vapor deposition film.
The gas barrier coating film may be a composite polymer layer in which one layer or two or more layers are laminated. Further, the dry film thickness may be 0.01-100 μm, preferably 0.01-50 μm. If the thickness after drying is 100 μm or less, the occurrence of cracks can be suppressed.
In the embodiment of the present invention, after providing a gas barrier coating film on the vapor deposition film, a vapor deposition film may be further provided, and the gas barrier coating film may be formed on the vapor deposition film in the same manner as described above. Thus, by increasing the number of stacked layers, it is possible to realize a stacked body that is further excellent in gas barrier properties.

(7) Print layer In the present invention, a desired print pattern layer can be formed between any of the layers constituting the packaging material. As the printed pattern layer, for example, when the base material layer is a paper base material, an ordinary gravure ink composition, offset ink composition, letterpress ink composition, screen ink composition on the paper base material. Products, other ink compositions, for example, gravure printing method, offset printing method, letterpress printing method, silk screen printing method, other printing methods, for example, from letters, figures, designs, symbols, etc. It can comprise by forming the desired printing pattern which becomes.

The printed layer can be printed on a plastic substrate when a desired printed pattern such as characters, figures, symbols, patterns, patterns, etc. is printed on the surface or when a transparent plastic substrate is used as the substrate layer. You may perform reverse printing.
Next, the present invention will be described with reference to examples.

Example 1
On the corona-treated surface of a 12 μm thick biaxially stretched polyethylene terephthalate film (Toyobo Co., Ltd., T-4102) with one side corona-treated, a two-component curable urethane adhesive (Rock Paint Co., Ltd., RU-40 / H4) 3 μm was applied, and 7 μm of aluminum foil (Toyo Aluminum Co., Ltd., 1N30) was laminated.

  Next, the laminated aluminum foil surface and a biaxially stretched polyethylene terephthalate (PET) film 12 μm (Toyobo Co., Ltd., T-4200) whose corona treatment was performed on both surfaces were laminated with a two-component curable urethane adhesive.

A curable polyolefin anchor coating agent containing a crosslinking agent (Unitika Ltd., Arrow Base SE-1205J2) was applied to the laminated PET treated surface by 0.3 μm, and this coated surface and a multilayer film of PE / EVOH / PE By laminating 40 μm (Tamapoly Co., Ltd., ZEA-104) through polyethylene (Japan Polyethylene Co., Ltd., LC600A) melt extruded so that the temperature under the die is 300 ° C. and the thickness is 15 μm. A pesticide packaging material was obtained.
(PET12 / DL / AL7 / DL / PET12 / AC agent of the present invention / LDPE10 / PEF40)

(Example 2)
Instead of the barrier sealant of Example 1, it was the same as Example 1 except that a non-adsorbing film 40 μm (DIC Corporation, MP3550) was used.
(PET12 / DL / AL7 / DL / PET12 / AC agent of the present invention / LDPE10 / non-adsorbing film)

(Example 3)
A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm and having one side corona-treated was used, and this film was mounted on a feed roll of a plasma chemical vapor deposition apparatus.
Next, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organosilicon compound, is supplied to the corona-treated surface of the above biaxially stretched polyethylene terephthalate film to form a vapor deposition film having a thickness of 200 nm. Plasma treatment was performed on the surface.

Next, according to the composition shown in Table 1 below, an ethyl silicate 40 having a composition b prepared in advance in an EVOH solution in which EVOH having a composition a (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water. Then, a hydrolyzate consisting of isopropyl alcohol, aluminum acetylacetone, and ion exchange water was added and stirred.
Further, a liquid mixture composed of polyvinyl alcohol having a composition c prepared in advance, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.

The plasma-treated surface was coated with the gas barrier composition produced above to form a gas barrier coating film having a thickness of 0.4 g / m ² (dry state) to produce a gas barrier laminated film.
Biaxially stretched polyethylene coated with 3 μm of a two-component curable urethane adhesive (Rock Paint Co., Ltd., RU-40 / H4) on the surface of the gas barrier coating film of the gas barrier laminate film formed as described above, and subjected to corona treatment on one side. A terephthalate film (Toyobo Co., Ltd., T-4102) was laminated.

Next, 0.3 μm of a curable polyolefin anchor coating agent (Unitika Ltd., SE-1205J2) was applied to the untreated surface of the gas barrier laminate film, and the coating surface and a PE / EVOH / PE multilayer film of 40 μm ( Tamapoly Co., Ltd., ZEA-104) was laminated via polyethylene (Nihon Polyethylene Co., Ltd., LC600A) melt-extruded so as to have a thickness of 15 μm at 300 ° C. to obtain a packaging material for agricultural chemicals. .
(PET12 / DL / AL7 / barrier coat / deposition surface / transparent deposition PET / AC agent of the present invention / PE / PEF)

Example 4
Instead of the barrier sealant of Example 3, it was the same as Example 1 except that a non-adsorbing film 40 μm (DIC Corporation, MP3550) was used.

(Example 5)
Instead of the barrier sealant of Example 1, it was the same as Example 1 except that a low-density linear polyethylene film 40 μm (Toyobo Co., Ltd., L-6100) was used.

(Example 6)
Instead of the barrier sealant of Example 3, it was the same as Example 3 except that a low-density linear polyethylene film 40 μm (Toyobo Co., Ltd., L-6100) was used.

(Comparative Example 1)
Two-component curable urethane adhesive (Lock), 12μm thick biaxially stretched polyethylene terephthalate film (Toyobo Co., Ltd., T-4102) with corona treatment on one side and aluminum foil (Toyo Aluminum Co., Ltd., 1N30) 7μm Lamination was performed through Paint Co., Ltd. (RU-40 / H4).
Next, a laminated aluminum foil surface and a biaxially stretched polyethylene terephthalate film 12 μm (Toyobo Co., Ltd., T-4200) having corona treatment on both surfaces were laminated with a two-component curable urethane adhesive.
Next, a packaging material of Comparative Example 1 was obtained by laminating a low density linear polyethylene film (Toyobo Co., Ltd., L6100) with a two-component curable urethane adhesive.
(PET12 / DL / AL7 / DL / PET12 / DL / PEF)

(Comparative Example 2)
It replaced with the low density linear polyethylene film of the comparative example 1, and it was the same as that of the comparative example 1 except having used the barrier sealant (Tamapoly Co., Ltd., ZEA-104).
(PET12 / DL / AL7 / DL / PET12 / DL / PEF)

(Comparative Example 3)
It replaced with the low density linear polyethylene film of the comparative example 1, and it was the same as that of the comparative example 1 except having used the non-adsorption film (DIC Corporation | KK, MP3550).
(PET12 / DL / AL7 / DL / PET12 / DL / PEF)

(Interlayer adhesion strength test)
The laminates of the above examples and comparative examples were cut into strips with a width of 15 mm, and the adhesion part between the polyester resin film layer and the polyolefin resin layer was 25 ° C. using a Tensilon tensile tester in accordance with JIS K6854. Under an atmosphere, the film was peeled in the direction of 90 degrees with a tensile speed of 50 mm / min, and the interlayer adhesion strength (initial) was measured.

  Next, 20 ml of agrochemical containing 48.0% by mass of glyphosate potassium salt, 0.2% by mass of ethylene glycol, and 52% by mass of other components was sealed in the packaging bag made of the laminates of the examples and comparative examples. It was stored for 30 days under dry conditions at 60 ° C. A strip-shaped test piece having a width of 15 mm was cut out from each packaging bag after 30 days storage, and the interlayer adhesion strength was measured in the same manner as described above. The results are shown in Table 2.

(Evaluation results)
As shown in Table 2, the packaging material of each example maintained good laminate strength even after 30 days.

The packaging material for agricultural chemicals of the present invention has improved resistance to various organic compounds, and can maintain stable laminate strength and sealing strength even after long-term storage of agricultural chemicals.
Moreover, according to the manufacturing method of this invention, the packaging material for agricultural chemicals which is excellent also in non-adsorbability and heat-fusibility can be manufactured easily.

1. Base material layer (polyester resin film layer)
2. 2. Anchor coat layer Sealant layer (polyolefin resin layer)
4). 4. Polyolefin resin film layer Barrier layer

Claims (9)

At least a base material layer comprising a polyester resin film layer, an anchor coat layer laminated adjacently on the polyester resin film layer, a polyolefin resin layer melt- extruded coated adjacently on the anchor coat layer, And, on the surface opposite to the surface adjacent to the anchor coat layer of the polyolefin resin layer , an organophosphorus / organic sulfur agrochemical packaging material further having a polyolefin resin film layer,
The anchor coat layer is an aqueous dispersion containing a polyolefin copolymer resin containing 0.01 to 5% by mass of an unsaturated carboxylic acid or an anhydride thereof and a crosslinking agent, but not containing a non-volatile aqueous additive. Then, a crosslinked cured layer obtained by applying an aqueous dispersion obtained by dispersing the polyolefin copolymer resin in an aqueous solvent so that the number average particle size thereof is 1 μm or less on the polyester resin film layer and drying it. der is,
The interlayer adhesive strength between the polyester resin film layer and the polyolefin resin layer after making a packaging container with the above packaging material, filling with agricultural chemicals and storing for 30 days under dry conditions at 60 ° C. is 4 N / 15 mm width. That's it,
The packaging material for agricultural chemicals described above.   The packaging material for agricultural chemicals of Claim 1 whose mass ratio of the said polyolefin copolymer resin and a crosslinking agent is 1: 1-10: 1 in the said aqueous dispersion.   The packaging material for agricultural chemicals according to claim 1 or 2, wherein the anchor coat layer has a dry thickness of 0.1 to 2 µm.   The packaging material for agricultural chemicals of Claim 3 which has a barrier layer further on the surface on the opposite side to the anchor coat layer lamination surface of the said polyester-type resin film layer.   It is a manufacturing method of the packaging material for agricultural chemicals of any one of Claims 1-3, Comprising: The said polyolefin-type by extrusion-coating polyolefin-type resin at the temperature of 300 degreeC or more on the said anchor coat layer. The said manufacturing method which provides a resin layer. It is a manufacturing method of the packaging material for agricultural chemicals of any one of Claims 1-4, Comprising: The said polyolefin resin formed by extrusion-coating a polyolefin resin at the temperature of 300 degreeC or more on the said anchor coat layer. The said manufacturing method of laminating | stacking the said polyolefin resin film layer by a sandwich lamination method through a layer.   The packaging container formed by stacking the packaging material for agricultural chemicals according to any one of claims 1 to 4 so that the polyolefin resin layer or the polyolefin resin film layer is the innermost layer and sealing the end thereof. .   The interlayer adhesive strength between the polyester-based resin film layer and the polyolefin-based resin layer after being filled with agricultural chemicals and stored for 30 days under dry conditions at 60 ° C is 4 N / 15 mm width or more. Packaging containers.   The packaging container according to claim 7 or 8, which is a packaging container for agricultural chemicals.

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