KR20190002845A - Adhesive compound of polymer film for flexible food package and a method of laminating - Google Patents

Abstract

The present invention relates to a polymer film adhesive compound for flexible food package and a laminating method, wherein when manufacturing a laminating film used for flexible food package, and each film is bonded, bonding is easily performed without immersing and coating an adhesive or other adhesive resin. More specifically, a commercial decline phenomenon between different films, commonly generated in case of bonding, is overcome to increase bonding strength.

Description

TECHNICAL FIELD The present invention relates to a polymer film for food packaging,

The present invention relates to a process for the production of a laminating film for use in a flexible food package, in which each film is impregnated with an adhesive or other adhesive resin, The present invention also relates to a method for manufacturing a polymer film for food packaging and a bonding composition for foods, which can increase the bonding strength by overcoming the miscibility between different kinds of films,

Lamination adhesives for food packaging are used when laminating together paper, plastic film, aluminum foil, etc., and must be strong, stable and hygienic.

The flexible food package is applied to the last stage of the food manufacturing process to protect the contents from mechanical force and high temperature environment during transport and storage and to prevent corruption, It is necessary to exhibit reliable gas barrier property from carbon dioxide gas and improve the merchantability of the food with colorful design printing.

Currently, the most widely used adhesives for food packaging are polyurethane reactive adhesives. Recently, there has been a growing interest in the safety of environmentally friendly packaging materials.

In response to these market demands, solvent type urethane adhesives are disappearing in the market in Europe and the United States, and non-solvent urethane adhesives are becoming popular.

Solvent-based adhesives have been mainly used in Korea until recently, but the use of solvent-free adhesives is increasing due to the increase of the interest in food safety of consumers and the strengthening of solvent regulations according to the Toxic Chemicals Control Act.

Solventless adhesives have no danger of fire or explosion as well as air pollution caused by solvents, and there is no need for solvent drying process. Lamination machine is small, solvent regeneration and incineration facilities are not required.

In addition, since the content of the residual solvent is low after the lamination operation, there is no fear of generation of odor, and the operation cost is lower than that of the solvent type adhesive, so that the application amount of the adhesive is lower than that of the solvent type adhesive.

The one-part type solvent-free adhesive developed for the first time in 1975 is a urethane prepolymer obtained by a reaction between a polyester polyol and isocyanate. The urethane prepolymer contains a reactive component, isocyanate, at the main chain end, React with moisture to form a cured structure.

One-component type solvent-free adhesives are applied at relatively high temperatures of 70 to 100 ° C in order to improve the permeability of the adhesive to the film and are mainly applied to laminate structures such as paper, film, foil and the like which are easy to penetrate water.

This is because it is not environmentally friendly because there is no need to dry the solvent during the operation because the diluting solvent is not used, and the production cost can be saved, and there is no residual solvent after bonding, contributing greatly to improvement of the odor of the packaging material.

However, in order to increase the mechanical workability during coating, the initial adhesive force is lower than that of the solvent type because the adhesive is designed to have a significantly lower molecular weight than the solvent type adhesive.

Therefore, there is a need for a dedicated machine for a solvent-free adhesive, which is capable of adjusting a suitable web tension so that wrinkles do not occur in the laminated laminate, and can apply a small coating weight.

In addition, when it is applied to a high-shear material such as a plastic film or an aluminum foil, moisture is not penetrated into the interior even if water is supplied from the outside, and the curing time of the product is prolonged.

In order to overcome the disadvantages of the one - component adhesive of moisture - curing type solubilizing agent, two - component type solvent - free adhesive was developed. The two-part system consists of a subject composed of an isocyanate prepolymer and a curing agent which is a hydroxy component.

They are all liquid at room temperature and can be used at temperatures between 25 ° C and 45 ° C, which is lower than the one-part solvent-free adhesives.

It is a two-liquid curing system that has a faster curing speed than a moisture curing system and exerts excellent adhesion even on various films, especially aluminum foil or aluminum evaporated film.

The two-component solvent-free adhesive is supplied through a two-component mixing machine which supplies the mixture of the base and the curing agent at a specified mixing ratio.

To reduce the adhesive thickness to 1.5-3.0 μm (g / m²), usually four or five rollers are used and the amount of adhesive applied is adjusted by adjusting the gap of the application rollers.

The working time is 30 to 120 minutes, which is shorter than the solvent type adhesive, but the adhesive is automatically supplied during the operation, so that the problem due to the increase in viscosity does not occur.

In general, two-component type solvent-free adhesive has lower molecular weight than solvent-type adhesive, so initial adhesive force is relatively low, so it is important to control film tension during lamination process. In a film having a low crystallinity such as polyamide, white polyethylene (PE), and ethylene vinyl acetate film due to the relatively high unreacted monomers contained therein, the poly It has a disadvantage that an anti-sealing phenomenon easily occurs due to the formation of a polyurea film.

Due to these limitations, careful consideration should be given to the application of solvent-free two-part adhesives for hazardous film combinations.

In addition, if the curing reaction of the solvent-free adhesive applied to the packaging material is not completely completed and the monomeric diisocyanate remains, it permeates through the packaging film layer and reacts with the moisture of the food content to form a primary aromatic amine (poly aromatic amine).

The European Food Safety Regulations '002/72 / EC and amendments' require that the content of primary aromatic amines in packaging materials be controlled to less than 10 ppb to ensure food safety.

Therefore, companies manufacturing laminating multilayered films for soft packaging are unable to meet the food safety requirements of end customers.

The prior art and the patent literature developed until now to improve these characteristics will be described as follows.

Korean Patent Laid-Open Publication No. 1019930006126 discloses a film-type adhesive in which a polyester-based adhesive and a polyamide-based adhesive are thermally melted and mixed at a weight ratio of 1: 2 to 2: 1. The above-described mixed adhesive prepared according to the present invention has advantages of a high adhesive strength, which is an advantage of a polyamide adhesive, and a high durability, which is an advantage of a polyester adhesive, Hot-press, and the adhesive is used in the form of a simple, low-pollution, low-energy small-sized adhesive in comparison with conventional polyester and polyamide single-component adhesives It has the advantage of being able to do. Korean Patent No. 101649359 discloses an epoxy resin composition for a film adhesive which has an excellent adhesive strength even at an extremely low temperature (minus 100 to 180 ° C) and can be cured within 5 hours even at a high temperature (80 ° C). The epoxy resin composition for the film adhesive contains two or more glycidyls in the molecule. 5 to 50 parts by weight, based on 100 parts by weight of the epoxy resin, of a reactive rubber containing a carboxyl acid at the terminal; 1 to 20 parts by weight of a dicyandiamide curing agent based on 100 parts by weight of the epoxy resin; Based on 100 parts by weight of the epoxy resin, 0.1 to 10 parts by weight of a urea curing accelerator; And a modified amine curing accelerator in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the epoxy resin and having a viscosity of 3,000 to 100,000 cps at 70 DEG C and a curing time of less than 5 hours at 80 DEG C . Korean Patent No. 100083993 discloses a high-melting-point copolymerized polyethylene terephthalate resin having a crystalline melting point of 130 to 200 ° C and a low melting point copolymerization polybutylene having a crystalline melting point of 50 to 120 ° C. Discloses a two-layer film-type polyester adhesive made of two layers of polybutylene terephthalate resin and a manufacturing method thereof. Since the double-layer film type polyester adhesive provided by the above invention contains both a high melting point resin and a low melting point resin, it is preferable to use a low melting point resin adhesive or a high melting point resin It has an advantage that it exhibits an effect superior to that of using an adhesive alone. WO 01997021779 (Jun. 19, 1997) discloses a fluorine-containing adhesive that maintains heat resistance, chemical resistance, weather resistance, and electrical insulation properties, and in particular, provides direct adhesion to metals or glass substrates, and an adhesive film And a laminate. The fluorine-containing adhesive is obtained by copolymerizing 0.05 to 30 mol% of at least one monomer among the fluorine-containing ethylenic monomers having a hydroxyl group and 70 to 99.95 mol% of at least one monomer of the fluorine-containing ethylenic monomer copolymerizable with the monomer And is produced from a fluorine-containing ethylene type polymer having a hydroxyl group. Korean Patent No. 100315133 discloses an epoxy resin composition comprising 45 to 55% by weight of an epoxy resin having an epoxy equivalent of 450 to 500 g / eq, 20 to 30% by weight of a rubber modified epoxy resin having an epoxy equivalent of 400 to 500 g / 10-20% by weight epoxy resin having an epoxy equivalent of 184-190 g / eq, and 3-9% by weight dicyandiamide as a curing agent. The film-type epoxy adhesive composition, A honeycomb sandwich panel having excellent performance and peel resistance can be easily manufactured. Korean Patent Laid-Open No. 1019980024413 discloses a polyvinyl alcohol, at least one polyaldehyde completely masked as a water-soluble hydrogen sulfide adduct having 3 or more carbon atoms, and at least one acidic A polyvinyl alcohol composition in the form of an aqueous solution comprising one or more compounds having the characteristics of being suitable for use as an adhesive and for use in a cast film. In International Patent Publication No. WO1993024583 (1993.12.09), acid component (A) 4,4'-oxyphthalic acid is anhydride and (B) 3,3 ', 4,4 '-Biphenyl carboxylic acid (3,3', 4,4'-benzopetonetetracarboxylic acid (3,3 ', 4,4'-biphenylcarboxylic acid) Siloxane compound represented by the following formula (1): wherein R1 and R2 are each an alkyl group having 2 to 4 carbon atoms, Is an aliphatic (C1-4) or aromatic group; R3, R4, R5 and R6 are each a monovalent aliphatic or aromatic group; And K is an integer of 1 to 20) and / or 2,2-bis (4- (4-aminophenoxy) phenyl) propane) (D) at least one of bis (4- (4-aminophenoxy) benzene) and / or dimethylphenylenamine is reacted to effect ring opening reaction of imide And has a glass transition temperature of 350 ° C or lower and is soluble in an organic solvent as a main component, and a method for producing the film adhesive. Japanese Patent No. JP-P-2012-236019 discloses an adhesive composition and an adhesive film capable of reducing the swelling by the resist solvent and the peeling from the support. Wherein the adhesive composition contains an elastomer having a styrene unit content of not less than 14% by weight and not more than 50% by weight and a hydrocarbon resin, wherein the content of the elastomer is not less than 50% by weight and not more than 99% by weight based on the total amount of the elastomer and the hydrocarbon resin % Or less, and the content of the hydrocarbon resin is 1 wt% or more and 50 wt% or less. International Patent Publication No. WO2012129489 (2012.09.27) provides a stretched film laminate adhesive, a method of using an adhesive to bond the substrate together, and an article of manufacture comprising an adhesive. Wherein the adhesive comprises a mtallocene catalyzed polyolefin copolymer having a density of greater than or equal to 0.870 g / cm < 3 > and a peak melting point of greater than 100 DEG C, a plasticizer having a number average molecular weight of greater than 1000 g / mol, , Has advantages such as high creep resistance and low plasticizer migration. In International Patent Publication No. WO2011155546 (Dec. 15, 2011), novel alkyl-modified polyvinyl alcohols capable of exhibiting excellent viscosity while maintaining high water solubility and having high water resistance in a cured state without using a special crosslinking agent, A composition containing polyvinyl alcohol, a thickener, a paper-applying agent, a coated paper, an adhesive and a film. Korean Patent No. 100262444 can exhibit excellent thermal adhesiveness even when another adhesive is not coated or other adhesive resin is not laminated, and a high friction coefficient phenomenon of a surface often occurs as a polymer film having heat adhesion property A thermally adhesive polymer film which can overcome the problem and can increase the heat bonding strength, and a method for producing the same. The present invention relates to a thermoplastic resin composition comprising a first polymer resin layer composed of a polyester containing 80% or more of ethylene terephthalate as a main repeating unit and an ethylene terephthalate-ethylene isophthalate copolymer as a main repeating unit A second polymer resin layer in which at least 70% by weight of a polyester is laminated on at least one side of the first polymer resin layer, a third polymer resin in the form of a copolymer polyester containing a hydrophilic group, and a colloidal silica is coated on the surface of the second polymer resin layer. Japanese Patent Publication No. JP-P-2005-00248154 discloses that although it is an adhesive on a film for fixing a semiconductor element, its thickness can be made thicker than the thickness of an electronic component provided on the substrate, The space formed between the substrate and the semiconductor element by the thickness of the electronic component provided on the substrate can be sufficiently filled with the adhesive agent for fixing the semiconductor element so that the semiconductor element can be efficiently and reliably adhered Which is capable of fixing a semiconductor element. Wherein the adhesive film is formed by laminating a plurality of films for an adhesive made of a material having a melt viscosity at 140 占 폚 of 50 Pa or less and having a thickness of 200 占 퐉 to 2000 占 퐉. to provide.

Accordingly, the polymeric film adhesive composition and the laminating method for softening pavement for food of the present invention solve the above problems and are capable of high-speed operation at 450 m / min or higher as compared with general two-part type solventless adhesives currently used in the market, A first object of the present invention is to provide a composition for an adhesive film which has high stability without causing unreacted monomers, and fast bonding speed.

Another object of the present invention is to provide a method for producing a polymer film for food packaging, which can be used as a packaging material for various food products and can also increase the heat bonding strength.

(2-hydroxyethyl) -2-imidazolidinone or 1- (2-2-hydroxyethyl) piperidine in a reactor equipped with a thermostat, a magnetic stirrer and a condenser. Imidazolidine precursor, imidazolidine precursor, and 600 to 1000 parts by weight of an acrylic monomer which is methyl acrylate, methyl methacrylate or tert-butyl methacrylate, 1 to 5 parts by weight of a condensation catalyst of potassium cyanate, potassium cyanide, potassium thiocyanate, p-nitrophenol, hydroquinone or hydroquinone monomethyl ether is added to the mixture which is stirred at a rate of 10 to 50 rpm while maintaining the temperature at 0 to 20 ° C 0.1 to 2.0 parts by weight of a polymerization inhibitor, phenothiazine, 10-methylphenotriazine, 2-chlorophenotriazine, 0.1 to 1.0 part by weight of a reaction stabilizer and 4-hydroxy-2,2,6,6-tetra Methylpiperidine 1-oxyl or 2,2,6,6-tetramethylpiperidine 1-oxy 0.005 to 0.02 parts by weight of a catalyst oxidizing agent are successively added thereto, and the mixture is reacted for 6 hours to 10 hours while maintaining the reaction temperature at 60 to 80 ° C., and then the temperature of the reactor is raised to 90 to 110 ° C. and reacted for 5 minutes to 60 minutes 2- (2-oxo-1-imidazolidinyl) ethyl acrylate, 2- (2-oxo-1- imidazolidinyl) ethyl methacrylate, 2- (2-oxo-1-imidazolidineethionyl) ethyl acrylate, and imidazolidine acrylate, which is 2- (2-oxo-1-imidazolidinethionyl) ethyl methacrylate;

20 to 30 parts by weight of an ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-methyl methacrylate, ethylene-vinyl acetate-ethyhexyl acrylate-ethylene-vinyl acetate copolymer and 20 to 30 parts by weight of an imidazoline acrylate- 1 to 20 parts by weight of imidazolidine acrylate and 0.1 to 5.0 parts by weight of an organic peroxide are sequentially introduced into a twin-screw extruder and melt-mixed at a temperature of 80 to 150 ° C for 1 to 30 minutes, A compatibilizing agent-introducing step of preparing a compatibilizing agent;

The compatibilizing agent is prepared by reacting 21.1 to 55 parts by weight of a compatibilizer prepared from the compatibilizing agent in the step of introducing the compatibilizing functional group and at least one of poly (butadiene) and polypentadiene, poly (isoprene), petroleum resin, poly (methylene- 30 to 60 parts by weight of a pressure-sensitive adhesive resin which is a resin, polydicyclopentadiene or hydrogensilicon polycyclopentadiene, 5 to 25 parts by weight of paraffin wax, Fischer-Tromsch wax, wax which is microcrystalline wax and 0.1 to 5.0 parts by weight of an antioxidant By weight into a mixing mixer such as a kneader mixer, a bus kneader or a Banbury mixer, and melt-kneading the mixture at a temperature of 80 to 200 DEG C for 10 to 60 minutes;

A pelletization step of making 56.2 to 145 parts by weight of the composition obtained in the melt kneading step into a composition pellet having a size of about 2 to 3 mm through a melt extrusion molding process using a uniaxial or biaxial extruder;

56.2 to 145 parts by weight of the pellets of the pelletizing step were placed in a single-screw or twin-screw extruded sheet hopper equipped with a sheet molding die, A temperature of 175 to 235 DEG C and an extrusion rate of 10 to 40 kg / hour;

The composition melt-extruded in the extrusion step is transferred between a film layer 1 made of a polymer resin supplied from a first take-off roller and a film layer 2 made of a polymer resin supplied from a second take-up roller, A laminating step of cooling to produce a laminating film;

The laminating film produced in the laminating step can be used as a wrapping material for various foodstuffs through a winding and wrapping step in which the laminating film is wound up on a bobbin in a roll state and a polymer film for foodstuff packaging can be easily manufactured .

As described above, the present invention is capable of high-speed operation at 450 m / min or higher in comparison with the laminating method using a conventional two-part type solvent-free adhesive currently used in the market, thereby reducing manufacturing cost and facilitating production, It is possible to easily produce a laminating adhesive film composition for packaging and an adhesive film for foods containing environmental and economic advantages such as high stability without generating monomers.

1 is a process flow diagram illustrating an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG.

(2-hydroxyethyl) -2-imidazolidinone or 1- (2-hydroxyethyl) -2-imidazolidine was added to the reactor equipped with a thermostat, a magnetic stirrer and a condenser. 200 to 300 parts by weight of a zazolidine precursor and 600 to 1000 parts by weight of an acrylic monomer which is methyl acrylate, methyl methacrylate or tert-butyl methacrylate are added, and the mixture is stirred at 10 to 50 rpm 1 to 5 parts by weight of a condensation catalyst of potassium cyanate, potassium cyanide, and potassium thiocyanate, 0.1 to 2.0 parts by weight of a polymerization inhibitor which is p-nitrophenol, hydroquinone or hydroquinone monomethyl ether, 0.1 to 1.0 part by weight of a reaction stabilizer which is phenothiazine, 10-methylphenothiazine, 2-chlorophenotriazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl or 2,2 , And 0.005 to 0.02 parts by weight of 6,6-tetramethylpiperidine-1-oxyphosphorus catalyst oxidizing agent The reaction was carried out for 6 hours to 10 hours while maintaining the reaction temperature at 60 to 80 ° C. The reaction temperature was raised to 90 to 110 ° C. and reacted for 5 minutes to 60 minutes to obtain 2- (2-oxo-1 (2-oxo-1-imidazolidinyl) ethyl acrylate, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate, 2- Preparing imidazolidine acrylate to produce imidazolidine acrylate which is 2- (2-oxo-1-imidazolidineethionyl) ethyl methacrylate;

20 to 30 parts by weight of an ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-methyl methacrylate, ethylene-vinyl acetate-ethyhexyl acrylate-ethylene-vinyl acetate copolymer and 20 to 30 parts by weight of an imidazoline acrylate- 1 to 20 parts by weight of imidazolidine acrylate and 0.1 to 5.0 parts by weight of an organic peroxide are sequentially introduced into a twin-screw extruder and melt-mixed at a temperature of 80 to 150 ° C for 1 to 30 minutes, A compatibilizing agent-introducing step of preparing a compatibilizing agent;

The compatibilizing agent is prepared by reacting 21.1 to 55 parts by weight of a compatibilizer prepared from the compatibilizing agent in the step of introducing the compatibilizing functional group and at least one of poly (butadiene) and polypentadiene, poly (isoprene), petroleum resin, poly (methylene- 30 to 60 parts by weight of a pressure-sensitive adhesive resin which is a resin, polydicyclopentadiene or hydrogensilicon polycyclopentadiene, 5 to 25 parts by weight of paraffin wax, Fischer-Tromsch wax, wax which is microcrystalline wax and 0.1 to 5.0 parts by weight of an antioxidant By weight into a mixing mixer such as a kneader mixer, a bus kneader or a Banbury mixer, and melt-kneading the mixture at a temperature of 80 to 200 DEG C for 10 to 60 minutes;

A pelletization step of making 56.2 to 145 parts by weight of the composition obtained in the melt kneading step into a composition pellet having a size of about 2 to 3 mm through a melt extrusion molding process using a uniaxial or biaxial extruder;

56.2 to 145 parts by weight of the pellets of the pelletizing step were placed in a single-screw or twin-screw extruded sheet hopper equipped with a sheet molding die, A temperature of 175 to 235 DEG C and an extrusion rate of 10 to 40 kg / hour;

The composition melt-extruded in the extrusion step is transferred between a film layer 1 made of a polymer resin supplied from a first take-off roller and a film layer 2 made of a polymer resin supplied from a second take-up roller, A laminating step of cooling to produce a laminating film;

The laminating film produced in the laminating step was wound up on a bobbin in a roll state, and the production of a polymer laminate film for food product packaging was completed.

The imidazolidine precursor in the imidazolidine acrylate preparation step serves to improve the adhesion with the laminating polymer film used for soft packaging, and 1- (2-hydroxyethyl) -2-imidazolidinone Or 1- (2-2-hydroxyethyl) -2-imidazolidine is used in an amount of 200 to 300 parts by weight.

At this time, when the amount is less than 200 parts by weight, a lot of impurities are formed. When the amount is more than 300 parts by weight, economical efficiency is low.

The acrylic monomer in the imidazolidine acrylate preparation step is preferably methyl acrylate, methyl methacrylate or tert-butyl methacrylate. In addition, butyl acrylate, butyl methacrylate Methacrylic acid, ethyl acrylate, and ethyl methacrylate may be used. However, the present invention is not limited thereto.

At this time, 600-1000 parts by weight of the acrylic monomer is used. When the amount is less than 600 parts by weight, the reactivity is poor. When the amount is 1000 parts by weight or more, the curing reaction proceeds and the gel content is increased.

The condensation catalyst in the step of preparing the imidazolidine acrylate is selected from the group consisting of potassium cyanate, potassium cyanide, potassium thiocyanate, sodium cyanide, copper (I) cyanide, and the like 1 to 5 parts by weight are used.

If the amount is less than 1 part by weight, the reactivity is lowered. If the amount is more than 5 parts by weight, the curing reaction proceeds and the gel content is increased.

As the polymerization inhibitor in the imidazolidine acrylate production step, 0.1 to 2.0 parts by weight of p-nitrophenol, hydroquinone or hydroquinone monomethyl ether is used, but the present invention is not limited thereto.

At this time, when the polymerization inhibitor is less than 0.1 part by weight, the curing reaction proceeds and the gel content is increased. When the amount is more than 2 parts by weight, the reactivity is decreased.

The reaction stabilizer in the imidazolidine acrylate production step is used in an amount of 0.1 to 1.0 part by weight, based on the weight of phenothiazine, 10-methylphenotriazine, and 2-chlorophenotriazine.

At this time, when the reaction stabilizer is less than 0.1 part by weight, the curing reaction proceeds and the gel content is increased. When the amount is more than 1 part by weight, the reactivity is lowered.

The catalyst oxidizing agent in the step of preparing imidazolidine acrylate may be 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl or 2,2,6,6-tetramethylpiperidine 1-oxy 0.005 to 0.02 parts by weight are used. In addition, 2,2,6,6-tetramethyl-1-piperidinyloxy polymer-bound (2,2,6,6-tetramethyl-1-piperidinyloxy) 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy), 4- (2-iodoacetamido) -2,2,6- 4- (2-iodoacetamido) -2,2,6,6-tetramethyl-1-piperidinyloxy) can also be used, but the present invention is not limited thereto.

At this time, when the amount of the catalyst oxidizing agent is less than 0.005 parts by weight, the curing reaction proceeds and the gel content increases. When the amount is more than 0.02 parts by weight, the reactivity decreases.

The ethylene-vinyl acetate-based copolymer in the step of introducing the compatibilizing functional group may be a copolymer of ethylene-vinyl acetate, ethylene-vinyl acetate-methyl methacrylate, ethylene-vinyl acetate-ethyhexyl acrylate, And the present invention is not limited thereto.

In addition to the ethylene-vinyl acetate copolymer, ethylene-butylacrylate, ethylene-methylacrylate, ethylene ethylacrylate, ethylene-methyl methacrylate, methylmethacrylate) copolymer can also be used.

At this time, the ethylene-vinyl acetate copolymer preferably has a hardness between 40 and 80 as Shore A.

At this time, when the hardness of the ethylene-vinyl acetate copolymer is less than 40, film formation is difficult, and when the hardness is 80 or more, the kneadability is poor.

The imidazolidine acrylate used in the step of introducing the compatibilizing functional group serves to improve adhesion with the laminating film used for soft packaging by reacting with the ethylene-vinyl acetate copolymer, and 2- (2-oxo- (2-oxo-1-imidazolidinyl) ethyl acrylate, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate, 2- , 2- (2-oxo-1-imidazolidineethionyl) ethyl methacrylate, and the like, or a combination of two or more thereof.

In addition to this, 2- (3- (4-methylpyrimidin-2-yl) ureido) ethyl methacrylate having a ureido-pyrimidyl functional group -yl) ureido) ethyl methacrylate, 4-amino-2-ureido-pyrimidine-5-carboxylic acid methacrylate, - (benzyl) -6-keto-2-ureido-pyrimidine-4-carboxylic acid methyl ester methacrylate, (1- (benzyl) -6-keto-2-ureido-pyrimidine-4-carboxylic acid methyl ester methacrylate) may be used, but the present invention is not limited thereto.

At this time, when the imidazolidine acrylate is less than 1 part by weight, the adhesive strength is lowered. When the imidazolidine acrylate is more than 20 parts by weight, the gelation reaction occurs and the workability is lowered.

The organic peroxide used in the step of introducing the compatible functional group chemically bonds the ethylene-vinyl acetate-based copolymer and the imidazolidine acrylate, and 0.1 to 5 parts by weight is used.

The organic peroxide is selected from the group consisting of benzoyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxy-2-ethylhexanoate (t- butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxybenzoate, peroxybenzoate, t-butyl peroxyisobutyrate, di (tert-butyl peroxide), t-butyl peroxyneodecanoate (t-butyl peroxyneodecanoate) ) May be used alone or in combination of two or more, and the present invention is not limited thereto.

At this time, when the organic peroxide is less than 0.1 part by weight, the reaction efficiency is lowered, and when it is more than 5 parts by weight, the economical efficiency is lowered.

The antioxidant used in the kneading step is used for the purpose of preventing the thermal oxidation of the composition which may occur during kneading, and poly (1,2-dihydro-2,2,4-trimethylquinoline) [poly (1,2- dihydro-2,2,4-trimethyl quinoline), pentaerythritol tetrakis (3,5-di-tert-butyl (3,5-di-tert- -4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-4-methyl phenol, tetrakis [methylene- Tetrakis [methylene-3- (3 '' hydroxyphenyl-propionate)] methane] or tris (2,4-di-tert- butylphenyl) Phosphatite], sulfanediyl-2,1-ethanediylbis 3- [4-hydroxy-3,5-bis (2-methyl-2 2-propanyl) phenyl] propanoate) and the like were prepared by the same method as in Synthesis Example 1, except that 2-methyl-2- Or in combination two or more of 0.1 to 5.0 parts by weight, but use, the invention is not limited to this.

When the amount of the antioxidant is less than 0.1 parts by weight, the polymer resin is oxidized during processing, and when the amount is more than 5.0 parts by weight, the economical efficiency is low.

The wax used in the kneading step is preferably paraffin wax, Fischer-Tromsch wax, microcrystalline wax and the like, but polyethylene wax, oxidized polyethylene wax and polypropylene wax may be used alone or in combination of two or more. .

At this time, 5 to 25 parts by weight of the wax is used. When the amount is less than 5 parts by weight, workability is poor. When 25 parts by weight or more is added, economical efficiency is low.

The polymeric film adhesive composition for laminating and laminating method for food according to the present invention will be described in more detail, and an embodiment thereof will be described as follows.

Hereinafter, the present invention will be described in more detail with reference to examples.

However, the scope of the present invention is not limited to the illustrated embodiments.

The components listed in Table 1 were mixed in the mixing ratios in the respective mixing ratios by the following manufacturing process to prepare a polymeric film adhesive composition for packaging for foods.

Examples of Polymer Film Adhesive Composition and Lamination Method for Soft Packaging for Food Raw material (parts by weight) Example One 2 3 4 5 6 7 8 9 10 11 12 Ethylene-vinyl acetate-based copolymer Ethylene-vinyl acetate 24 - - 24 - - 24 - - 24 - - Ethylene-vinyl acetate-methyl methacrylate - 24 - - 24 - - 24 - - 24 - Ethylene-vinyl acetate-ethylene glycol hexyl acrylate - - 24 - - 24 - - 24 - - 24 Imidazolidine acrylate 2- (2-oxo-1-imidazolidinyl) ethyl acrylate 5 5 5 - - - - - - - - - 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate - - - 5 5 5 - - - - - - 2- (2-oxo-1-imidazolidineethionyl) ethyl acrylate - - - - - - 5 5 5 - - - 2- (2-oxo-1-imidazolidineethionyl) ethyl methacrylate - - - - - - - - - 5 5 5 Organic peroxide t-butylperoxy-3,5,5-trimethylhexanoate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Adhesive resin Polydicyclopentadiene, 50 50 50 50 - - 50 - - 50 - - Hydrogenated policyclopentadiene - - - - 50 - - 50 - - 50 - Petroleum resin - - - - - 50 - - 50 - - 50 Antioxidant Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Wax Fisher-Tromsch wax 20 20 20 20 20 20 20 20 20 20 20 20 Sum 100 100 100 100 100 100 100 100 100 100 100 100 Test Items Adhesive strength (N / 25mm) 0.45 0.42 0.40 0.41 0.40 0.40 0.44 0.42 0.42 0.41 0.40 0.40 Amine detection X X X X X X X X X X X X

Process for producing 2- (2-oxo-1-imidazolidinyl) ethyl acrylate

270 parts by weight of 1- (2-hydroxyethyl) -2-imidazolidinone and 620 parts by weight of methyl acrylate were added to a reactor equipped with a thermostat, a magnetic stirrer and a condenser, To the mixture stirred at a speed of 30 rpm, 2.7 parts by weight of potassium cyanate, 0.6 part by weight of hydroquinone, 0.3 part by weight of phenothiazine and 0.015 part by weight of 4-hydroxy-2,2,6,6-tetramethylpiperidine- And then reacted for 8 hours while maintaining the reaction temperature at 70 ° C. Then, the reactor temperature was raised to 100 ° C, and the reaction was carried out for 20 minutes and purified.

Process for producing 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate

270 parts by weight of 1- (2-hydroxyethyl) -2-imidazolidinone and 620 parts by weight of methyl methacrylate were added to a reactor equipped with a thermostat, a magnetic stirrer and a condenser, and then the reactor temperature was maintained at 10 ° C , 2.7 parts by weight of potassium cyanide, 0.6 part by weight of hydroquinone monomethyl ether, 0.3 part by weight of 10-methylphenothiazine, and 0.2 part by weight of 2,2,6,6-tetramethylpiperidine 1-oxy And then reacted for 10 hours while maintaining the reaction temperature at 70 ° C. Then, the reactor temperature was raised to 100 ° C and the reaction was carried out for 15 minutes and purified.

Preparation of 2- (2-oxo-1-imidazolidineethionyl) ethyl acrylate [

To a reactor equipped with a thermostat, a magnetic stirrer and a condenser, 270 parts by weight of 1- (2-2-hydroxyethyl) -2-imidazolidine and 270 parts by weight of methyl acrylate were added, , 2.7 parts by weight of potassium thiocyanate, 0.6 part by weight of p-nitrophenol, 0.3 part by weight of 2-chlorophenotriazine and 2,2,6,6-tetramethylpiperidine 1 -Oxy were sequentially added and reacted for 9 hours while maintaining the reaction temperature at 70 ° C. Then, the reactor temperature was raised to 100 ° C, and the reaction was carried out for 20 minutes and purified.

Method for producing 2- (2-oxo-1-imidazolidineethionyl) ethyl methacrylate

270 parts by weight of 1- (2-2-hydroxyethyl) -2-imidazolidine and 620 parts by weight of tetra-butyl methacrylate were added to a reactor equipped with a thermostat, a magnetic stirrer and a condenser, Was stirred at a rate of 40 rpm while maintaining the temperature at 10 DEG C, 2.7 parts by weight of potassium cyanide, 0.6 part by weight of hydroquinone monomethyl ether, 0.3 part by weight of phenothiazine, and 4 parts by weight of 4-hydroxy-2,2,6,6- And 0.015 part by weight of tetramethylpiperidine 1-oxyl were successively added thereto, and the mixture was reacted for 9 hours while maintaining the reaction temperature at 70 占 폚, followed by elevating the reactor temperature to 100 占 폚 for 20 minutes.

Examples 1 to 12 Manufacturing method

24 parts by weight of ethylene-vinyl acetate copolymer, 5 parts by weight of imidazolidine acrylate and 0.5 part by weight of organic peroxide were sequentially added to a twin-screw extruder and melt-kneaded at 120 to 180 ° C for 10 minutes and pelletized And processed into a compatibilizer pellet having a size of about 2 to 3 mm. 31 parts by weight of the compatibilizer pellets, 50 parts by weight of the pressure-sensitive adhesive resin, 20 parts by weight of the wax and 0.5 parts by weight of the antioxidant were sequentially added to a 20 L kneader mixer and melt kneaded at 160 DEG C for 10 minutes to obtain a melt- A single-shaft sheet machine having a sheet molding die capable of being formed into a composition pellet having a size of about 2 to 3 mm through a melt extrusion molding process at a temperature of 150 to 220 캜, And the temperature zone was separated into a continuous single cylinder under the condition of cylinder 1: 200 ° C, cylinder 2: 210 ° C, and cylinder 3: 210 ° C, and at a temperature of 215 ° C, Lt; / RTI > / hour.

The adhesive film thus prepared was stretched at 150 x 150 mm Hot-pressing for 10 seconds at a temperature of 120 ° C and a pressure of 2 atm for 10 seconds. After cooling to room temperature, the adhesive strength was measured using a universal tester. The results are shown in Table 1 below. Respectively.

As shown in <Table 1>, it can be confirmed that the adhesive bonding laminating film for food according to the embodiment of the present invention is superior to the conventional urethane type adhesive agent (~ 0.35 N / 25 mm).

By using the polymeric film adhesive composition for laminating film for packaging of the present invention and the laminating method, it is possible to perform a high-speed operation at a rate of 450 m / min or more in the production of the product, thereby facilitating production cost reduction and production, It is possible to easily manufacture a laminating adhesive laminating film for foodstuffs containing environmental and economic advantages such as high stability and the like.

Claims (3)

200 to 300 parts by weight of imidazolidine precursor and 600 to 1000 parts by weight of an acrylic monomer were added to the reactor and the mixture was stirred at a rate of 10 to 50 rpm while maintaining the temperature of the reactor at 0 to 20 ° C. 0.1 to 2.0 parts by weight of a polymerization inhibitor, 0.1 to 1.0 part by weight of a reaction stabilizer and 0.005 to 0.02 part by weight of a catalytic oxidant are successively added, and then the reaction is carried out for 6 to 10 hours while maintaining the reaction temperature at 60 to 80 ° C Preparing an imidazolidine acrylate by raising the temperature of the reactor to 90 to 110 ° C and reacting for 5 minutes to 60 minutes to prepare imidazolidine acrylate;
20 to 30 parts by weight of an ethylene-vinyl acetate copolymer, 1 to 20 parts by weight of imidazolidine acrylate prepared in the step of preparing imidazolidine acrylate, and 0.1 to 5.0 parts by weight of an organic peroxide are sequentially introduced into a twin screw extruder Mixing the mixture at a temperature of 80 to 150 ° C for 1 to 30 minutes, and then producing a compatibilizing agent having a size of about 2 to 3 mm;
21.1 to 55 parts by weight of a compatibilizer prepared in the step of introducing the above-mentioned compatibility functional group, 30 to 60 parts by weight of a pressure-sensitive adhesive resin, 5 to 25 parts by weight of a wax and 0.1 to 5.0 parts by weight of an antioxidant are sequentially introduced into a mixer, Kneading the kneaded mixture at a temperature of 10 to 60 minutes;
A pelletization step of making 56.2 to 145 parts by weight of the composition obtained in the melt kneading step into a composition pellet having a size of about 2 to 3 mm through a melt extrusion molding process using a uniaxial or biaxial extruder;
56.2 to 145 parts by weight of the pellets of the pelletizing step were placed in a single-screw or twin-screw extruded sheet hopper equipped with a sheet molding die, A temperature of 175 to 235 DEG C and an extrusion rate of 10 to 40 kg / hour;
The composition melt-extruded in the extrusion step is transferred between a film layer 1 made of a polymer resin supplied from a first take-off roller and a film layer 2 made of a polymer resin supplied from a second take-up roller, A laminating step of cooling to produce a laminating film;
Wherein the laminating film produced in the laminating step is wound and wound on a bobbin in a roll state. The method according to claim 1,
The imidazolidine precursor in the preparation step of the imidazolidine acrylate is preferably 1- (2-hydroxyethyl) -2-imidazolidinone or 1- (2-hydroxyethyl) -2- And the azeotropic monomer is any one of methyl acrylate, methyl methacrylate and tert-butyl methacrylate, and the condensation catalyst is any one of potassium cyanate, potassium cyanide, and potassium thiocyanate , The polymerization inhibitor is any one of p-nitrophenol, hydroquinone and hydroquinone monomethyl ether, the reaction stabilizer is any one of phenothiazine, 10-methylphenotriazine and 2-chlorophenotriazine, Is either 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl or 2,2,6,6-tetramethylpiperidine 1-oxy, 2- (2-oxo- -Imidazolidinyl) ethyl acrylate, 2- (2-oxo-1-imidazolidinyl) ethyl 2- (2-oxo-1-imidazolidineethionyl) ethyl acrylate, imidazolidine acrylate is 2- (2-oxo-1-imidazolidineethionyl) Ethyl methacrylate;
The ethylene-vinyl acetate-based copolymer in the step of introducing the compatibilizing functional group is any one of ethylene-vinyl acetate, ethylene-vinyl acetate-methyl methacrylate and ethylene-vinyl acetate-ethythexyl acrylate;
The pressure-sensitive adhesive resin in the melt-kneading step for melt-kneading may be any one selected from the group consisting of poly (butadiene), polypentadiene, poly (isoprene), petroleum resin, poly (methylene- Diene, and hydrogenated polycyclopentadiene. The method for producing a polymer film for food soft packaging according to claim 1, 20 to 30 parts by weight of an ethylene-vinyl acetate copolymer, 1 to 20 parts by weight of imidazolidine acrylate, 0.1 to 5.0 parts by weight of an organic peroxide, 30 to 60 parts by weight of a pressure-sensitive adhesive resin, 5 to 25 parts by weight of a wax, And 0.1 to 5 parts by weight of an antistatic agent.

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