KR102067263B1 - Adhesive film for eco-adhesive body - Google Patents

Abstract

The present invention relates to an adhesive film for an eco-adherend and a production method of an adhesive. The adhesive film is an adhesive film for an eco-printing layer comprising a base layer, a primer layer, and an adhesive layer, wherein the adhesive layer comprises: 70 to 96 wt% of ethylene vinyl acetate (EVA); 2 to 15 wt% of polyester polyol; and 2 to 15 wt% of a polyurethane resin reacting isocyanate with polyfunctional polyol.

Description

Adhesive film for eco-adhesive body {Adhesive film for eco-adhesive body}

The present invention relates to an adhesive film for eco-adhesives, and more particularly, to an adhesive film for eco-adhesives that can improve bonding strength when laminating a film on an adherend printed with eco-friendly ink.

Laminating is the use of an adhesive to bond the film on the surface of the adherend to protect the printed layer on the adherend, and to deliver the image of the printed content sufficiently to enhance the visual effect while increasing the water resistance and durability of the adherend for a long time. It is a work to prevent damage to printed materials during distribution.It is divided into oil-based laminating method and water-based laminating method according to the type of adhesive used at this time, and it has high transparency and gloss according to the type of film used. Falling, subtle and graceful is called matte laminating.

In addition, the aqueous laminating method can be divided into dry and wet, the wet is suitable for the substrate is a large and dark image or the printed material is a lot of powder, and the thin paper may be deformed because the deformation may occur.

Dry can be thin paper that is difficult to wet, and thick prints of 300 g / m ² or more are difficult to wet, so dry. Wet requires a certain time of natural drying after laminating, and dry can be produced immediately because the machine itself has a drying device.

The oily laminating method has good physical properties such as water resistance, durability, chemical resistance, and color sharpness, compared to the aqueous laminating method.However, the oily laminating method has been widely adopted.However, in the oily laminating method, organic solvents such as benzene and toluene are used. Due to the use of the water quality and air pollution as well as the volatile organic solvents generated during work, especially due to problems such as fire risks and harm to humans in recent years, the world-wide environmentally friendly laminating method of water-based laminating The method has been widely adopted, and in Korea, the adoption of an aqueous laminating method is becoming common in consideration of adverse effects on the environment of components such as benzene and toluene.

On the other hand, when laminating and coating a film made of PP, PET, PA, etc. on the printing surface of the adherend printed with eco-friendly ink such as palm oil or soybean oil, adhesive resin mixed with PE (Polyethylene) and EVA (Ethylene Vinyl Acetate) Toxic solvent adhesives are used because of poor adhesion. However, since the solvent adhesive has a problem of environmental pollution due to its toxicity and the price is also high, there is a problem of price increase, and thus an adhesive having excellent adhesive performance and eco-friendly is required.

Document 1: Patent Publication No. 10-1548971 Document 2: Registered Patent Publication No. 10-0549709

The present invention is to provide an adhesive film for an eco-adhesive which can firmly laminate the film on the printing surface of the adherend printed with eco-friendly ink by mixing a functional additive with the eco-friendly ink on the PE or EVA base. The purpose.

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The technical problem to be achieved in the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned above may be clearly understood by those skilled in the art from the following description. There will be.

The present invention as a means for solving the above problems, an adhesive film for an eco-adhesive comprising a substrate layer, a primer layer and an adhesive layer, the adhesive layer is 70 to 96% by weight of ethylene vinyl acetate (EVA); 2 to 15% by weight of polyester-based polyol; And it provides an adhesive film for eco-printing paper comprising 2 to 15% by weight of a polyurethane resin reacted with isocyanate to the polyfunctional polyol.

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Preferably, the polyester-based polyol is one selected from the group consisting of dibasic acids such as adipic acid, maleic acid, fumaric acid, sebacic acid, azelaic acid, succinic acid, terephthalic acid, isophthalic acid, phthalic acid, and dialkyl ester compounds thereof. More than one acid and ethylene glycol, diethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, polytetramethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol , 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3-methyl-1,8-octanediol, 3,3'-dimethylolheptane, polyoxy The polyol or a copolymer thereof obtained by condensation of at least one alcohol selected from the group consisting of ethylene glycol, polyoxypropylene glycol and polytetramethylene ether glycol may have a number average molecular weight of 400 to 10,000.

Preferably, the polyester-based polyol may be obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) and the like.

Preferably, the polyol is adipic acid (Adipic acid), Sveric acid (Sbelic acid), Abelic acid (Abelic acid), Sebacic acid (Sebacicacid), Dodecandionic acid (Dodencandionic acid), and Trimeric acid (Trimeric acid) At least one dicarboxylic acid selected from the group consisting of, wherein the isocyanate is an aromatic diisocyanate, diphenylmethane diisocyanate (MDI: Diphenyl methanediisocyanate), toluene diisocyanate (TDI: Toluene diisocyanate), hexamethylene diisocyanate ( One or more diisocyanate compounds selected from the group consisting of HDI: Hexamethylene diisocyanate), dicyclohexylmethane diisocyanate (H12MDI), and isophorone diisocyanate (IPDI), wherein the equivalent ratio of polyol and diisocyanate May be from 0.90 to 1.05.

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According to an embodiment of the present invention, by applying an adhesive made of environmentally friendly components while being strongly adhered to the eco-adhered body, it is possible to solve environmental pollution problems and price problems.

The effects of the present invention are not limited to the above-described effects, but should be understood to include all the effects deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a block diagram of an adhesive film according to an embodiment of the present invention
Figure 2 is a flow chart for explaining the adhesive manufacturing method of the present invention

Hereinafter, with reference to the accompanying drawings will be described the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, coupled)" with another part, it is not only "directly connected" but also "indirectly connected" with another member in between. "Includes the case. In addition, when a part is said to "include" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, action, component, part, or combination thereof described on the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

1 is a block diagram of an adhesive film according to an embodiment of the present invention.

According to Figure 1, the adhesive film of one embodiment of the present invention is laminated on the printing surface of the eco-adhered body, it can be firmly laminated on the printing surface printed with eco-friendly ink, such as palm oil or soybean oil.

The adhesive film of one embodiment may include a base layer 10, a primer layer 20, and an adhesive layer 30. Here, the primer layer 20 may be excluded.

The base layer 10 is a base film, and the type thereof is not particularly limited. For example, an olefin-based film such as polypropylene or polyethylene; Polyester-based films such as polyethylene terephthalate; Polycarbonate film; Polyvinyl chloride film; Polytetrafluoroethylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film ethylene-vinyl acetate copolymer film; Ethylene-propylene copolymer film; Or a mixture of one or more kinds of ethylene-ethyl acrylate copolymer films and the like. The heterogeneous mixing of the base film at this time means the film which a base film consists of two or more laminated | multilayer film among each film mentioned above, or is manufactured from the copolymer of each resin mentioned above.

Here, the primer layer 20 may be formed on the surface of the substrate layer 10, and may be corona treatment, etching treatment, or UV treatment.

The composition of the primer layer 20 may include a polyvinyl alcohol compound including acetoacetyl group, 2) an acrylate compound containing at least two vinyl groups, and 3) a basic catalyst.

The polyvinyl alcohol-based compound including the acetoacetyl group may be prepared by reacting the polyvinyl alcohol-based compound with diketene. For example, the polyvinyl alcohol-based compound containing the acetoacetyl group is dispersed in a polyvinyl alcohol-based compound in a solvent such as acetic acid, a method of adding diketene thereto, the dimethylformamide or dioxane polyvinyl alcohol-based compound It can be prepared by dissolving in advance in a solvent such as a solvent, adding diketene to the solvent, or directly contacting the gaseous or liquid diketene with the polyvinyl alcohol compound.

It is preferable that the acetoacetyl group modification degree of the polyvinyl alcohol-type compound containing the said acetoacetyl group is 0.1-40 mol%, and it is more preferable that it is 1-10 mol%. The acetoacetyl group denaturation can be measured by NMR.

2) As the acrylate compound containing at least two vinyl groups, 1,6-hexadiol diacrylate (1,6-hexadiol diacrylate), ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol Diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, neopentylglycol diacrylate, and the like, and 1,6-hexadiol diacrylate (1,6-hexadiol diacrylate) is more preferred. Preferred but not limited thereto.

2) The acrylate containing at least two vinyl groups may be added in an amount of about 0.1 to 2 equivalents to the acetoacetyl group in the polyvinyl alcohol compound including an acetoacetyl group, and more preferably added in an amount of 0.9 to 1.2 equivalents. It is preferable to show good adhesive force.

The adhesive layer 30 may include a polyurethane resin obtained by reacting isocyanate with a polyester-based polyol and a polyfunctional polyol on an ethylene vinyl acetate (EVA) base.

Here, the ethylene vinyl acetate (EVA) is preferably 70 to 96% by weight, 2 to 15% by weight of the polyester-based polyol, 2 to 15% by weight of the polyurethane resin reacted with isocyanate to the polyfunctional polyol. .

Adhesive force falls that the said ethylene vinyl acetate (EVA) is 70 weight% or less, and kneading property falls that it is 96 weight% or more. Adhesive force falls that the said polyester-type polyol is 2 weight% or less, and kneading property falls that it is 15 weight% or more. If the polyurethane resin which made isocyanate react with the said polyfunctional polyol is 2 weight% or less, adhesive force will fall, and if it is 15 weight% or more, kneading property will fall.

The ethylene vinyl acetate resin is the main component of the main material, it is possible to keep the strength of the adhesive produced by the cohesive strength is constant. Conventionally, an epoxy resin was used as a main component of an adhesive. When an epoxy resin was used, volatile organic compounds such as solvent or benzene toluene were released, which had a detrimental effect on the environment and human body. However, the present invention can solve problems such as environmental problems by excluding the epoxy resin.

The said polyester polyol is preferable at the point which is excellent in adhesiveness with the base material layer 10 compared with polyols, such as a polycarbonate polyol and a polycaprolactone polyol.

The polyester-based polyols are prepared by condensation of an acid with an alcohol, for example, dibasic acids such as adipic acid, maleic acid, fumaric acid, sebacic acid, azelaic acid, succinic acid, terephthalic acid, isophthalic acid, phthalic acid, and dialkyl esters thereof. At least one acid selected from the group consisting of ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, polytetramethylene glycol, neopentyl glycol, 1,3- Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3-methyl-1,8 Polyols by condensation of at least one alcohol selected from the group consisting of -octanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol and polytetramethylene ether glycol; or Of a copolymer.

The polyester-based polyol may be a product obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone and poly (β-methyl-γ-valerolactone).

The polyester polyol preferably has a number average molecular weight of 500 to 100,000, more preferably 1,000 to 30,000. When the number average molecular weight is less than 500, the cohesive force of the adhesive may be small, thereby reducing the adhesive strength. In addition, when the number average molecular weight is more than 100,000, the viscosity may be excessively increased or gelation may be caused.

The polyurethane resin may be prepared by reacting isocyanate with a polyfunctional polyol. Adhesives based on polyurethane resins are one component of adhesives that can meet various needs with advantages such as adhesion performance, flexibility, low temperature properties, high cohesiveness and curing rate control. The urethane structure is easily wetted on most material surfaces and can induce hydrogen bonds. Molecular size can permanently penetrate the porous material surface. If the surface of the material has active hydrogen, urethane can form covalent bonds with the surface of the material.

Leisurely, the polyol may be adipic acid, Svelic acid, Abelic acid, Sebacic acid, Dodencandionic acid, and Trimeric acid. At least one dicarboxylic acid selected from the group consisting of, diol is ethylene glycol (Ethylene glycol), diethylene glycol (Diethyleneglycol), 13-butanediol (Butane diol), 1,4-butanediol (Butane diol ) At least one polyfunctional alcohol selected from the group consisting of 1,5-pentane diol, 1,6-hexanediol, and neopropanediol, and polytetramethylene ether glycol Was prepared and used.

Isocyanates include diphenylmethane diisocyanate (MDI: Diphenyl methane diisocyanate), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI: Hexamethylene diisocyanate), and dicyclohexylmethane diisocyanate (H12MDI). ), And isophorone diisocyanate (IPDI: Isoporone diisocyanate).

The equivalent ratio of polyol and diisocyanate is 0.90 to 1.05.

The weight ratio is 5 to 95 parts by weight of isocyanate based on 25 to 90 parts by weight of polyol, ethylene glycol (Ethyleneglycol), diethylene glycol, 13-butanediol, 1,4-butanediol 1 It can be used in 10 to 50 parts by weight of one or more chain extenders consisting of diols, including, 5-pentanediol, 1,6-hexanediol, and neopropanediol.

The thickness of the adhesive layer () is not particularly limited, but may be, for example, 1 μm to 200 μm, preferably 5 μm to 100 μm. When the said thickness is less than 1 micrometer, there exists a possibility that a high temperature stress relaxation effect and embedding property may fall, and when it exceeds 200 micrometers, economic efficiency will fall.

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Figure 2 is a flow chart for explaining the adhesive manufacturing method of the present invention.

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According to Figure 2, the adhesive production method of the present invention in one step, ethylene vinyl acetate (EVA) 70 to 96% by weight; 2 to 15% by weight of polyester-based polyol; And 2 to 15% by weight of the polyurethane resin reacted with isocyanate to the polyfunctional polyol in a mixer and mixing for 10 to 20 minutes (S100).

Step 2 is a step (S200) of injecting and extruding the mixture into a single or twin screw type extruder, and molding the mixture to a predetermined diameter by an extruder.

In the third step, the extrudate is cut into a predetermined size by an underwater cutter or strand pelletizer while cooling in water having a water temperature of 5 to 30 ° C. (S300). Here, the underwater cutting machine is a known mechanical device, which is connected to an extruder for supplying a resin melt, and is an underwater cutting device that cuts the extrudate extruded from the extruder into granules while cooling it in water.

Step 4 is a step (S400) for sorting the extrudate cut in the step by size by a mesh screener.

Step 5 is a step (S500) of drying the extruded granules by introducing air into the hopper while the extruded granules selected in the above step are put into the hopper of the packaging machine.

Here, for good extrusion of the extruder screw RPM is 200 ~ 500, the temperature of the extruder is preferably 140 ~ 200 ℃.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples merely illustrate the contents of the present invention and do not limit the protection scope of the present invention.

Preparation of adhesive film for eco adherend

Laminating a polyvinyl alcohol compound containing acetoacetyl group, an acrylate compound containing at least two vinyl groups and a primer layer comprising a basic catalyst and an adhesive layer on a substrate layer of polyethylene film, wherein the adhesive layer is ethylene vinyl acetate (EVA) 82% by weight, 9% by weight of a polyester-based polyol, 9% by weight of a polyurethane resin in which isocyanate was reacted with a polyfunctional polyol were added to a mixer and mixed for 10 to 20 minutes to prepare an adhesive.

An adhesive was prepared in the same manner as in Example 1, except that 15% by weight of the polyester-based polyol and 15% by weight of the polyurethane resin in which the isocyanate was reacted with the polyfunctional polyol were used as the adhesive layer.

An adhesive was prepared in the same manner as in Example 1, except that 1% by weight of the polyester-based polyol and 1% by weight of the polyurethane resin in which the isocyanate was reacted with the polyfunctional polyol were used as the adhesive layer.

Comparative Example 1

Instead of the polyurethane resin in which isocyanate was reacted with ethylene vinyl acetate (EVA), polyester-based polyol, and polyfunctional polyol, 39% by weight of polyethylene (PE) and 61% by weight of EVA (ethylene vinyl acetate) were mixed. Prepared an adhesive in the same manner as in Example 1.

Comparative Example 2

Instead of the polyurethane resin obtained by reacting isocyanate with ethylene vinyl acetate (EVA), polyester-based polyol, and polyfunctional polyol, an adhesive resin in which 59% by weight of polyethylene (PE) and 41% by weight of EVA (ethylene vinyl acetate) was mixed An adhesive was prepared in the same manner as in Example 1 except that the solvent was coated on the solvent.

Adhesive composition ratio (unit: weight%) EVA
(Ethylene Vinyl Acetate) Polyester polyol Isocyanate
Other
PE EVA Example 1 82 9 9 - - Example 2 70 15 15 - - Example 3 98 One One - - Comparative Example 1 - - - 39 61 Comparative Example 2 - - - 59 41

Experimental Example

Physical properties of the adhesives obtained in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2.

Adhesive force (gf / 15mm)

The film adhesive obtained in the above Examples and Comparative Examples was put in a pilot coating facility (60 mm single screw extruder, L / D = 305, die 650 mm), extrusion temperature 140 ~ 230 ℃, die temperature 230 ℃, screw rotation speed 20rpm conditions In, the extrusion coating was carried out on the film substrate. At this time, the thickness of the coating layer was 10 ㎛.

Thereafter, using a laminating apparatus at a temperature of 100 ℃, on the extrusion coated adhesive on the film base material, after laminating the printing surface of the printing paper by measuring the peel strength through a Peel Test according to ASTM D1876 standards The adhesion of the printing paper was checked.

division Adhesive force (g / 15mm) Example 1 225 Example 2 245 Example 3 202 Comparative Example 1 152 Comparative Example 2 173

As shown in Table 2, Examples 1 to 3 measured the adhesive force when the content ratio of isocyanate to polyester-based polyol and polyfunctional polyol in a state in which ethylene vinyl acetate (EVA) was fixed at 82% by weight As a result, when the content ratio of isocyanate to polyester-based polyol and polyfunctional polyol was relatively high, it was found that the adhesion (adhesive strength) was finely strong.

On the other hand, as in Comparative Examples 1 and 2, in the case of adhesives composed of only PE and EVA, the solvent-coated adhesive is relatively strong, but it is confirmed that the adhesive strength is significantly lower than that of Examples 1 to 3 in general. Could.

Although the above-described embodiment has been described with respect to the preferred embodiment of the present invention, it is noted that the present invention is not limited thereto and may be implemented in various forms without departing from the technical spirit of the present invention.

10: base material layer 20: primer layer
30: adhesive layer, second adhesive layer 40: first adhesive layer

Claims (8)

An adhesive film for an eco printing layer comprising a base layer, a primer layer and an adhesive layer,
The adhesive layer is 70 to 96% by weight of ethylene vinyl acetate (EVA); 2 to 15% by weight of polyester-based polyol; And 2 to 15% by weight of a polyurethane resin obtained by reacting isocyanate with the polyfunctional polyol.
delete delete The method according to claim 1,
The polyester-based polyol is at least one acid selected from the group consisting of dibasic acids such as adipic acid, maleic acid, fumaric acid, sebacic acid, azelaic acid, succinic acid, terephthalic acid, isophthalic acid, phthalic acid, and dialkyl ester compounds thereof. Ethylene glycol, diethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, polytetramethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 3-methyl-1,8-octanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, Polyol or a copolymer thereof by condensation reaction of one or more alcohols selected from the group consisting of polyoxypropylene glycol and polytetramethylene ether glycol, wherein the number average molecular weight is 400 to 10,000 for an eco adherend Adhesive film.
The method according to claim 1,
Polyester-based polyols are obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) and the like.
The method according to claim 1,
The polyol is a group consisting of adipic acid, averic acid, Sbelic acid, Abelic acid, Sebacic acid, Dodecandionic acid, and trimeric acid. At least one dicarboxylic acid selected from,
The isocyanate is diphenylmethane diisocyanate (MDI: Diphenyl methanediisocyanate), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI: dicyclohexylmethane diisocyanate), which is an aromatic diisocyanate. And at least one diisocyanate compound selected from the group consisting of isophorone diisocyanate (IPDI),
The equivalent ratio of the polyol and diisocyanate is an adhesive film for eco-adhesives, characterized in that 0.90 to 1.05. delete delete

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