JPH11147290A - Packing laminated film and packing laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film and a laminate excellent in environmental properties and work environmental properties, holding conventional boiling resistance, adhesiveness, transparency and gas barrier capacity and suitable for various gas barrier packings. SOLUTION: In a packing laminated film wherein an anchor agent and polyvinylidene chloride are laminated, a main agent of the anchor coat agent is a water dispersible polyester polyurethane resin with a glass transition temp. of 60 deg.C or higher and a curing agent thereof is a water dispersible polyisocyanate compd. A packing laminate is formed by using this film. The water dispersible polyisocyanate compd. is an aliphatic polyisocyanate compd. with an average number of functional groups of 3-5 and an isocyanate group content of 3-50 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film for packaging which is excellent in environmental properties and working environment, excellent in boiling water suitability, adhesiveness, transparency and gas barrier properties.

[0002]

2. Description of the Related Art Conventionally, polyester and polypropylene films have been widely used for packaging because of their excellent film-forming properties, transparency, moldability and moisture-proof properties.
Among them, polyester biaxially stretched film has heat resistance,
Because of its excellent gas barrier properties, it is laminated with an unstretched polyolefin film and used as a heat-resistant base material for packaging materials.

In order to improve the gas barrier performance of a packaging material, a heat-resistant substrate such as a polyvinylidene chloride (hereinafter abbreviated as PVDC) coat layer or a polyester film or a polypropylene film on which an aluminum (Al) vapor-deposited layer is laminated. It is common for materials to be used as part of the construction of the packaging material. More specifically, the structure of heat-resistant base material / PVDC / adhesive layer / unstretched polyolefin film or heat-resistant base material / print layer / adhesive layer / PVDC
Alternatively, configurations such as Al / heat-resistant base material / adhesive layer / unstretched polyolefin film are known.

However, in a configuration using PVDC, PVDC usually has a weak adhesive strength to a heat-resistant substrate, and therefore,
Surface treatment such as corona discharge treatment and PVDC for heat-resistant substrates
Generally, an anchor coat agent having good adhesiveness is applied, and PVDC is applied thereon. As the anchor coating agent, a solvent-type anchor coating agent diluted with an organic solvent such as ethyl acetate or toluene has been used. Although these solvent-type anchor coating agents exhibit high performance in terms of adhesiveness, heat resistance, water resistance, etc., they use a large amount of organic solvents, which leads to safety problems, environmental pollution problems, and resource saving. It was not preferable from a point.

[0005] To improve these, Japanese Patent Publication No. 57-262 has been proposed.
No. 32, Japanese Patent Publication No. 1-19343, Japanese Patent Publication No. 55
JP-A-3150 proposes an aqueous anchor coating agent that does not use an organic solvent, but has insufficient heat resistance such as deterioration in transparency and decrease in adhesiveness during boiling sterilization. Japanese Patent Application Laid-Open No. 6-346019 proposes a coating agent comprising an aqueous acrylic-modified polyurethane resin, but has insufficient adhesiveness and transparency to be used as a packaging material for boiling sterilization.

[0006]

SUMMARY OF THE INVENTION The present invention provides a water-dispersed anchor coating agent which does not use an organic solvent and which has not been achieved by the prior art. An object of the present invention is to provide a laminated film for packaging having excellent adhesiveness, transparency, and gas barrier properties of a later film.

[0007]

According to the present invention, there is provided a packaging laminate film and a packaging laminate using the same, wherein the main component of the anchor coating agent is a glass transition temperature of 60 ° C.
The above water-dispersible polyester-based polyurethane resin is characterized in that the curing agent of the anchor coating agent is a water-dispersible polyisocyanate compound.

[0008] The packaging laminate of the present invention is characterized in that another film is laminated on the polyvinylidene chloride coated surface of the above-mentioned packaging laminated film.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The film used for the laminated film for packaging of the present invention is a heat-resistant base material of a biaxially stretched film of a polyolefin resin, a nylon resin, a polyethylene terephthalate resin, and a polyethylene naphthalate resin.

In order to smoothly apply the anchor coating agent to the surface of the heat-resistant substrate, it is preferable to employ a corona discharge treatment on the surface of the heat-resistant substrate as a preliminary treatment. The atmosphere gas at the time of the corona discharge treatment may be any of air, carbon dioxide gas, or a mixed system of nitrogen / carbon dioxide gas, particularly a mixed gas of carbon dioxide gas or nitrogen / carbon dioxide gas (volume ratio = 95/5 to 50/50). It is preferable to carry out corona treatment in the above). Additives can be added to the heat-resistant base material as needed as long as the effects of the present invention are not impaired. Contains additives normally used in resins such as anti-blocking agents, nucleating agents, ultraviolet absorbers, heat stabilizers, antioxidants, weathering stabilizers, antistatic agents, and inorganic and organic fillers. Can be. As the antiblocking agent, inorganic particles and / or crosslinked organic particles or a mixture thereof is more preferable. The particle shape is preferably spherical, and the particle size is preferably in the range of 1 to 6 μm.

The main component of the anchor coating agent used in the laminated film for packaging of the present invention must be a water-dispersible polyester-based polyurethane resin and its glass transition temperature must be 60 ° C. or higher. is there. When the glass transition temperature is lower than 60 ° C., the drying temperature of water is 100 ° C.
This is not preferable because the temperature is as high as not less than ° C., because the adhesive strength to PVDC is likely to be adversely affected.

The water-dispersed polyester-based polyurethane resin refers to a resin comprising an emulsifier and an aqueous polyester-based polyurethane emulsion. The emulsifier is obtained by reacting a polyisocyanate with an alkoxypolyalkylene ether glycol and a dialkanolamine.
Examples of the polyisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, 1,3-cyclohexylene diisocyanate, and 1,4-cyclohexylene. Diisocyanate, hydrogenated xylylene diisocyanate,
Isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-
4,4′-dicyclohexylmethane diisocyanate,
Alicyclic diisocyanate such as 1,5-tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate,
2,4′-diphenylmethane diisocyanate, 2,
2'-diphenylmethane diisocyanate, 3,3'-
Dimethyl-4,4'-diphenylene diisocyanate,
Aromatic diisocyanates such as 1,5-naphthalene diisocyanate, xylylene diisocyanate, aromatic aliphatic diisocyanates such as tetramethyl xylylene diisocyanate, 2,4,6-triisocyanate toluene,
2,4,6-triisocyanate diphenyl ether,
Triisocyanates such as tri (isocyanatephenyl) methane and tri (isocyanatephenyl) thiophosphite; biuret-type polyisocyanates derived from 3 moles of diisocyanate isocyanate and 1 mole of water; formed by trimerization of diisocyanates. Isocyanurate type polyisocyanate, polymethylene polyphenyl polyisocyanate by-produced during production of diphenylmethane-4,4'-diisocyanate, and glycols, triols or polyester polyols;
Examples thereof include adduct-type polyisocyanates and polyisocyanates such as isocyanate prepolymers obtained by adding the above polyisocyanates to polyether polyols and the like, and mixtures thereof. Suitably, diisocyanates are preferred.

Examples of the alkoxypolyalkylene ether glycol include methoxy polymethylene ether glycol, ethoxy polymethylene ether glycol,
Methoxy polyethylene ether glycol, ethoxy polyethylene ether glycol, methoxy polybutylene ether glycol, ethoxy polybutylene ether glycol, or the like can be used.

As the dialkanolamine, dimethanolamine, diethanolamine, dipropanolamine, diisopropanolamine, diethanolaniline and the like can be used.

The aqueous polyester-based polyurethane emulsion comprises a polyester polyol composed of dimethylolpropionic acid, isophthalic acid, sebacic acid, neopentyl glycol and ethylene glycol as a polyol component, and tolylene diisocyanate and hydrogenated xylylene diisocyanate as a triisocyanate component. It is a polyester-based polyurethane emulsion obtained from the mixture.

[0016] In addition to the aqueous polyester-based polyurethane emulsion, other aqueous emulsions such as polyvinyl chloride emulsion, urethane acrylic emulsion,
Silicone acrylic emulsion, vinyl acetate acrylic emulsion, acrylic emulsion, and latex, for example, styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, chloroprene latex, polybutadiene Latex rubber latex, polyacrylate latex,
Polyvinylidene chloride latex, polybutadiene latex, or carboxyl-modified or water-soluble substances of these latexes, for example, polyvinyl alcohol, water-soluble ethylene-vinyl acetate copolymer, polyethylene oxide, aqueous acrylic resin, aqueous apoxy resin, aqueous cellulose derivative, Although an aqueous polyester and an aqueous lignin derivative may be used, an aqueous polyester-based polyurethane emulsion is preferred from the viewpoint of adhesion to a substrate.
Carboxyl group in the emulsion resin, having an organic acid group such as a sulfonic acid group, amines, those which form a salt with a basic substance such as an alkali metal and are dispersed, and a hydroxyl group in the emulsion resin, It has a functional group capable of reacting with an isocyanate group such as an amino group and a carboxyl group.

The curing agent for the anchor coating agent used in the laminated film for packaging of the present invention must be a water-dispersed polyisocyanate compound. As the water-dispersed polyisocyanate compound, the same polyisocyanate as used in the production of the emulsifier is used, and aliphatic polyisocyanates such as tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate are preferred.

The aliphatic polyisocyanate composition used in the packaging laminate film of the present invention has an average number of functional groups of 3 to 5
Is preferably less than 3, the dispersibility in water and water resistance may be poor, and if it exceeds 5, the dispersibility in water may be poor. The isocyanate group content of the aliphatic polyisocyanate composition is preferably in the range of 3 to 50% by weight. If it is less than 3% by weight, dispersibility in water and water resistance may be poor, and if it exceeds 50% by weight, dispersibility in water may be poor. The anchor coating agent is composed of a water-dispersible polyester-based polyurethane resin as a main component and a water-dispersible polyisocyanate compound as a curing agent, and
It is used by mixing at a ratio of 0 to 0.2 and diluting with water to an appropriate concentration. In order to obtain stable coating quality after mixing, the pot life at a temperature of 25 ° C is preferably 6 hours or more. In order to smoothly apply the anchor coating agent on the surface of the heat-resistant base material, a corona discharge treatment is applied to the film surface as a preliminary treatment, or it is chemically inert with the mixed aqueous solution of the anchor coating agent. It is preferable to use a suitable antifoaming agent in combination. The antifoaming agent promotes wetting of the anchor coating agent to a heat-resistant base material that can lower the surface tension. For example, an antifoaming agent of a lower alcohol type, an organic polar compound type, a mineral oil type, a silicone type, etc. Is preferred. As a lower alcohol antifoaming agent,
Organic polar compound antifoaming agents such as methanol, ethanol, isopropanol and n-butanol include amino alcohol, octyl alcohol, isobutyl carbitol, tributyl phosphate, oleic acid, tall oil, metal soap, surfactant (for example, sorbitan Lauric acid monoester, sorbitan lauric acid triester, polyethylene glycol fatty acid ester, pluronic nonionic surfactant, etc.), polypropylene glycol, acrylic vinyl polymer, etc. Silicone-based antifoaming agents such as surfactants of oil and fatty acid metal salts, such as silicone oil, silicone resin, modified silicone, silicone and surfactant, silicone and inorganic powder, etc. it can. Among them, a silicone-based antifoaming agent is preferably used because it is effective in a very small amount.

In addition, as long as the effects of the present invention are not impaired in the mixed aqueous solution of the anchor coating agent, if necessary,
Additives can be added. For example, rosin ester emulsion, terpene resin emulsion, tackifier such as petroleum resin emulsion, aminosilane, epoxy silane, silane coupling agent such as acrylic silane, carboxymethylcellulose, thickener such as polyvinylpyrrolidone, silica, talc, mica, Fillers such as calcium carbonate, crosslinking agents such as carbodiimide and epoxy resin, lubricants such as stearic acid and zinc stearate, and catalysts such as tertiary amines and metal salts of organic acids can be used.

In the present invention, the surface free energy of the coated surface of the anchor coating agent used for the laminated film for packaging is preferably 45 mN / m or more. 45mN
If it is less than / m, application unevenness is likely to occur at the time of PVDC application, and the adhesive strength and gas barrier properties may decrease. In addition, increasing the free energy of the film surface to 45 mN / m or more by performing corona discharge treatment on the surface coated with the anchor coat can be preferably employed in order to improve the adhesion of PVDC. The atmosphere gas at the time of the corona discharge treatment may be any of air, carbon dioxide gas, or a mixed system of nitrogen / carbon dioxide gas, particularly a mixed gas of carbon dioxide gas or nitrogen / carbon dioxide gas (volume ratio = 95/5 to 50/50). It is preferable to perform the corona treatment in ()) because the free energy of the anchor coat surface increases to 45 mN / m or more.

On the PVDC-coated surface of the laminated film for packaging of the present invention, it is preferable to laminate another film such as a non-stretched polyolefin film as a heat seal layer by extrusion laminating a polyolefin resin or an adhesive. . The laminate for packaging is sealed by overlapping a heat seal layer, and is used as a packaging bag.

Next, the manufacturing method of the laminated film for packaging and the laminated body for packaging of the present invention will be described with reference to an example of laminating in order of heat-resistant substrate / anchor coat / PVDC, but the present invention is not limited to this example. It is not something to be done. The anchor coating agent may be applied to a commercially available heat-resistant substrate, or may be applied to a substrate formed in-line.

First, a polyethylene terephthalate resin dried at a temperature of 170 ° C. for 3 hours or more is supplied to an extruder and melted at a temperature of 270 to 300 ° C. to obtain a filtration filter. The sheet is formed, wound around a metal drum maintained at 25 to 40 ° C., and cooled and solidified to form a sheet. This sheet was heated to a temperature of 95 ° C., stretched 3.2 times in the longitudinal direction, cooled and then led to a tenter-type stretching machine, heated to a temperature of 125 ° C., and stretched 3.2 times in the width direction. Heat-treating for 6 seconds while giving 5% relaxation in the width direction at a temperature of 230 ° C., then blowing normal temperature air onto the film, cooling to a temperature of 40 ° C.,
The surface on which the anchor coat is applied is subjected to corona discharge treatment in air or a mixed gas atmosphere of nitrogen / carbon dioxide gas so that the free energy of the sheet surface is 45 mN / m or more, and a water-dispersed polyester polyurethane resin as a main component, a curing agent Water is added to a 1: 1 anchor coating agent as a solid content of a water-dispersed polyisocyanate compound to form a 5% by weight aqueous solution. The aqueous solution is applied, dried at a temperature of 120 ° C. for 30 seconds, and wound into a roll. Thereafter, a water-dispersed PVDC is applied to the anchor coat surface, dried at a temperature of 120 ° C. for 30 seconds, wound up in a roll form, and then the rolled sheet is left in an atmosphere of 30 ° C. or more for 48 hours or more to form PVD.
C can be crystallized to obtain a laminated film for packaging. Next, the PVDC-coated surface of the laminated film for packaging is subjected to a corona discharge treatment in the air or a mixed gas atmosphere of nitrogen / carbon dioxide gas, and the free energy of the surface is reduced to 45 mN /
m or more, linear low-density polyethylene is laminated by an extrusion lamination method, and can be wound into a roll to obtain a laminate for packaging.

[Method of measuring characteristic values] The characteristic values of the present invention are measured by the following measuring methods.

(1) Glass transition temperature: Seiko In
Using a thermal analyzer S11 manufactured by Strument, the water content of the base material of the anchor coat is evaporated by a vacuum drier, and the solid content of 5 mg of the base material of the anchor coat is heated from room temperature at a heating rate of 20 ° C./min. At that time, the center temperature of the inflection region was defined as the glass transition temperature.

(2) Pot life of anchor coating agent:
After mixing the main component of the anchor coat and the curing agent, the time at which the residual ratio of isocyanate in the prepared aqueous solution at 25 ° C. was less than 60% exceeded 3 hours, was evaluated as ○, and that of less than 3 hours was evaluated as x.

(3) Surface free energy: The packaging laminated film was peeled off, and 1.5 μl of a solution of pure water, ethylene glycol, formaldehyde and methylene iodide was dropped on the surface of the peeled anchor coat layer with a syringe. Using a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd., the contact angle was measured at a room temperature of 23 ° C. and an atmosphere of 65% humidity, and the surface free energy was determined as follows.

The surface free energy (γ _S ) of a solid is determined indirectly by measuring the contact angle (θ) with a liquid having a known surface force (γ _L ). The surface free energy of the solid is separated into three components: a dispersive force component (γ _S ^d ), a polar force component (γ _S ^p ), and a hydrogen bond component (γ _S ^h ).
Expression (1) (extended Fowkes expression) obtained by extending the owkes expression is used.

Γ _SL = γ _S + γ _L −2 (γ _S ^d γ _L ^d ) ^1/2 −2 (γ _S ^p γ _L ^p ) ^1/2 −2 (γ _S ^h γ _L ^h ) ^1/2 (1) Equation γ _SL is the tension at the interface between a solid and a liquid.

The state when the liquid droplet is in contact with the smooth solid surface at the contact angle (θ) is represented by the Young's equation of the equation (2).

Γ _S = γ _SL + γ _L COSθ (2) Expression (1) and Expression (2) are combined to obtain Expression (3).

(Γ _S ^d γ _L ^d ) ^1/2 + (γ _S ^p γ _L ^p ) ^1/2 + (γ _S ^h γ _L ^h ) ^1/2 = γ _L (1 + COSθ) / 2 (3) Formula The contact angles of the anchor coat surface of the liquids of pure water, ethylene glycol, formaldehyde, and methylene iodide were measured three times for each liquid, and the average value was substituted into the equation (3). A simultaneous equation consisting of four equations is established for each liquid, and the quaternary simultaneous equation is solved to obtain a dispersion force component, a polar force component of the surface free energy of the anchor coat surface,
Hydrogen bond components were separated and determined, and the total value was shown as surface free energy in the unit of mN / m.

(4) Adhesive strength: For a laminated film for packaging,
Takeda Pharmaceutical Co., Ltd. polyurethane adhesive (base agent "Takelac" A-971 / curing agent "Takenate" A-3 = 9
/ 1 was applied using a coating bar to a thickness of about 4 μm, and a non-stretched polypropylene film was attached.
Aged at 40 ° C. for 2 days to cure. After cutting out this laminated film to a width of 15 mm, it is heated at 90 ° C. for 20 minutes.
A boiling treatment was performed for a minute. Then, the heat-resistant base material side and the non-stretched polypropylene film side are reinforced with cellophane tape, and the adhesive surface is peeled off by 90 degrees at a pulling speed of 100 mm / min using Orientec UCT-100 “Tensilon”. The applied force was shown as an adhesive strength in a unit of N / cm.

(5) Heat seal strength: An adhesive was applied to the laminated film for packaging in the same manner as the sample for which the adhesive strength was measured, bonded to a non-oriented polypropylene film, and then aged and cured. . Thereafter, the unstretched polypropylene films are superimposed and heat-sealed at a sealing temperature of 115 ° C., a sealing pressure of 98 kPa and a sealing time of 1 second by a double-sided heating method using a heat sealer to obtain a 150 mm long, 100 mm wide. A three-sided sealed pouch is made, 200 g of a mixture of vinegar / salad oil / ketchup having a weight ratio of 1/1/1 is put into the pouch, and after sealing, the pouch is boiled in hot water of 90 ° C. for 20 minutes. went. After cutting out the heat seal part of this pouch to a width of 15 mm, Orientec UCT-
Using a 100 type "Tensilon", pulling speed 300mm
/ Min, the force required when peeling the seal face 90 degrees
Those with 1.3 N / cm or more were evaluated as ○, those with 0.65 N / cm or less were evaluated as x, and those between them were evaluated as Δ.

(6) Transparency (haze) of film: A sample cut out of the above pouch was subjected to ASTM D1003.
It measured according to -52.

(7) Gas barrier properties: Water vapor transmission rate (moisture proof) A sample cut from the pouch is a water vapor transmission rate meter “PERMATRAN” W3 / manufactured by Modern Control.
Using No. 31, the value measured under the conditions of 100% humidity and 37.8 ° C. temperature is shown in units of g / m ² · day.

B. Oxygen Permeability A sample cut from the above pouch was measured using an oxygen permeability meter “OXTRAN” -100 manufactured by Modern Control Co. under a condition of 0% humidity and a temperature of 23 ° C.
/ M ² · day · MPa.

(8) Comprehensive evaluation: Regarding coatability, environmental workability, film characteristics after boiling, and practicality as a packaging film, excellent was evaluated as O, slightly poor as Δ, and poor as X. .

[0039]

Next, the configuration and effects of the present invention will be described with reference to the following examples.
This will be described more specifically.

Example 1 A polyethylene terephthalate film "Lumirror" type P60 (thickness: 12 μm) manufactured by Toray Industries, Inc. was subjected to corona discharge treatment with a surface free energy of 45 mN / m or more as a heat-resistant substrate of the laminated film for packaging of the present invention. A water-dispersible polyester polyurethane resin having a glass transition temperature of 90 ° C. is used as a main component of an anchor coating agent, and a water-dispersible polyisocyanate compound having an isocyanate group content of 19% by weight (1,6 hexamethylene diisocyanate and methoxypolyethylene) is used as a curing agent. Using an aliphatic isocyanate obtained from ether glycol) as a solid content, adding pure water to a weight ratio of 1: 1 to form a 5% by weight aqueous solution, and using a coating bar to coat the film on the corona discharge treated surface of the film. , Dried at 120 ° C for 30 seconds, It was coated with the anchor coating agent of .4μm. Thereafter, polyvinylidene chloride (Kurehalon latex DO821S manufactured by Kureha Chemical Industry Co., Ltd.) is applied to the anchor coat surface and dried at 120 ° C. for 30 seconds to obtain a polyvinylidene chloride coating laminated film having a coating thickness of about 4 μm. Was. Next, a polyurethane adhesive manufactured by Takeda Pharmaceutical Co., Ltd. (base agent "Takelac" A-971 / hardener "Takenate" A-3 = 9 /
One solution was coated with a coating bar and the adhesive thickness was about 4μ.
m, and bonded to a non-stretched polypropylene film, aged at 40 ° C. for 4 days or more and cured to obtain a packaging laminate. Thereafter, the unstretched polypropylene films are superimposed on each other, and the three sides are sealed under the conditions of a sealing temperature of 115 ° C., a sealing pressure of 98 kPa, and a sealing time of 1 second by a double-side heating method of a heat sealer, thereby forming a pouch. A mixture having a vinegar / salad oil / ketchup weight ratio of 1/1/1 was added, and one was sealed under the above conditions. Put this pouch in hot water at 90 ° C for 20
After boiling for a minute, the contents were taken out and the inside of the pouch was washed, and the pouch was cut out to evaluate the film characteristics.

Example 2 As polyvinylidene chloride, IXAN manufactured by Solvay was used.
A laminated film for packaging and a laminated body for packaging were obtained in the same manner as in Example 1 except that PA232 was used.

Example 3 A laminate film for packaging and a laminate for packaging were prepared in the same manner as in Example 1 except that a water-dispersible polyisocyanate (Desmodur DA manufactured by Sumitomo Bayer Polyurethanes, Inc.) was used as a curing agent for the anchor coating agent. I got

Example 4 A laminate film for packaging and a laminate for packaging were prepared in the same manner as in Example 1 except that a water-dispersible polyisocyanate (SBU isocyanate 0772, manufactured by Sumitomo Bayer Polyurethanes) was used as a curing agent for the anchor coating agent. I got a body.

Comparative Example 1 A curing agent obtained from an aromatic isocyanate, tolylene diisocyanate, was used in place of the curing agent of Example 1 as a curing agent for the anchor coating agent.

Comparative Example 2 A laminate film for packaging and a laminate for packaging were obtained in the same manner as in Example 1 except that the curing agent for the anchor coat agent was not added.

Comparative Example 3 A laminate film for packaging and a laminate for packaging were obtained in the same manner as in Example 1 except that a water-dispersible polyester-based polyurethane resin having a glass transition temperature of 10 ° C. was used as a main component of the anchor coat agent. .

Comparative Example 4 A packaging laminate film and a packaging laminate were obtained in the same manner as in Example 1 except that a water-dispersible polyester-based polyurethane resin having a glass transition temperature of 45 ° C. was used as a main component of the anchor coating agent. .

Comparative Example 5 A laminated film for packaging and a laminated body for packaging were obtained in the same manner as in Example 1 except that an ethyl isocyanate solution of tolylene diisocyanate of an aromatic isocyanate was used as a curing agent for the anchor coating agent.

Table 1 shows the quality evaluation results of the laminated film for packaging and the laminated product for packaging.

As a result, the laminated films for packaging and the laminated products for packaging obtained in Examples 1 to 3 were excellent in transparency, adhesion and gas barrier properties.

On the other hand, since the aqueous solution of the anchor coat prepared in Comparative Example 1 has a short pot life, the coating film becomes uneven in the latter half of application to the film, and a laminated film for packaging and a laminated product for packaging are obtained. Did not. Moreover, although the laminated film for packaging and the laminated body for packaging obtained in Comparative Example 2 to Comparative Example 4 are excellent in transparency, they are inferior in adhesiveness and gas barrier properties, so that they are practical when used as gas barrier packaging bags. The film was inferior.

The packaging laminate film and the packaging laminate obtained in Comparative Example 5 are excellent in transparency, adhesiveness and gas barrier properties. However, since an organic solvent is used at the time of coating, the organic solvent has an odor. , The working ring was bad.

[0053]

[Table 1] Water vapor permeability measurement condition: temperature 37.8 ° C, humidity 100% Oxygen permeability measurement condition: temperature 23 ° C, humidity 0%

[0054]

The laminate film for packaging obtained by the present invention and the laminate for packaging using the same can be prepared by using an aqueous dispersion type as a dispersion medium of a base material of an anchor coat agent and a curing agent, thereby obtaining an organic solvent type film. As compared with the above, it is possible to provide films and laminates which are more excellent in environmental property and work environment property, retain the conventional boiling water resistance, adhesiveness, transparency and gas barrier properties, and are suitable for various packaging applications.

Claims (4)

[Claims] 1. A laminated film for packaging in which an anchor coating agent and polyvinylidene chloride are laminated, wherein the main component of the anchor coating agent is a water-dispersed polyester polyurethane resin having a glass transition temperature of 60 ° C. or higher, and the anchor coating agent is Wherein the curing agent is a water-dispersed polyisocyanate compound. 2. The water-dispersed polyisocyanate compound has an average number of functional groups of 3 to 5 and an isocyanate group content of 3 to 5.
The laminated film for packaging according to claim 1, which is an aliphatic polyisocyanate compound of 50% by weight. 3. The laminated film for packaging according to claim 1, wherein the surface free energy of the coated surface of the anchor coating agent is 45 mN / m or more. 4. An anchor coating agent and polyvinylidene chloride are laminated, and the main component of the anchor coating agent is a water-dispersed polyester polyurethane resin having a glass transition temperature of 60 ° C. or higher, and the curing agent of the anchor coating agent is water. A packaging laminate, characterized in that another film is laminated on the polyvinylidene chloride-coated surface of the packaging laminate film which is a dispersion-type polyisocyanate compound.