KR100855213B1 - The simultaneous bonding and embossing method of the biodegradable resins sheets - Google Patents

Abstract

A method for simultaneously combining and embossing biodegradable resin sheets is provided to prevent interlayer delamination or bubbles as well as damage to an emboss. A method for simultaneously combining and embossing biodegradable resin sheets comprises a step of combining a first biodegradable resin sheet(1) with an acryl resin sheet(2) or a second biodegradable resin sheet(1݆) by allowing the sheets to pass through drum rollers having surface temperature of 40°C to 150°C while an upper heater applies radiant heat of 40°C to 100°C to the sheets. The biodegradable resin sheet is made of, PLA(Poly Lactic Acid), PGA(Poly Glycolic Acid), PCL(Poly Caprolactone), fatty polyester resin, PHB(Poly Hydroxyl Butyric Acid) or D-3-hydroxy butyric acid. A mixture, which is obtained by adding aziridine of 5wt% to 40wt% to hydrogenous ink having no well-known pigment, is coated on a third biodegradable resin sheet(1") to form a primer layer.

Description

The simultaneous bonding and embossing method of the biodegradable resins sheets}

The present invention relates to a method of simultaneously processing the laminated and embossing of the biodegradable resin sheet, more specifically, polylactic acid (PLA), polyglycolic acid (poly glycolic acid, PGA), poly caprolactone (poly caprolactone) , PCL), aliphatic polyester resin, polyhydroxy butyric acid (PHB) or D-3-hydroxy butyric acid as a main material biodegradable resin sheet, Pass the acrylic resin sheet or the biodegradable resin sheet of the same type as the biodegradable resin sheet through a drum roller, and the surface temperature of the drum roller is 40 to 150 ° C, and the sheet is passed through radiating heat of 40 to 100 ° C with an upper heater. On the other biodegradable resin sheet, a mixture of 5 to 40% by weight of aziridine was added to the weight of the aqueous ink excluding a known pigment, and the mixed mixture was applied with a primer layer of a matte coating. Embossing is carried out by passing through the sheet laminated with the embossing, and the embossing temperature is 50-150 ° C., the embossing pressure is 20-60 kgf / cm 2, and the temperature of the front heater is 80-200 ° C. under radiant heat conditions. In this way, not only the lamination between the biodegradable resin sheets is easily performed, but also the embossing formed is not lost or damaged, and the lamination and embossing simultaneous processing methods of the biodegradable resin sheets, which can easily perform lamination and embossing without generating cracks, It is about.

In general, synthetic resins, which are polymer compounds obtained by artificially synthesizing raw materials such as coal, petroleum, and natural gas, which are fossil fuels, have characteristics such as processability, strength, hardness, corrosion resistance, weather resistance, water resistance, and durability, and are free of coloring and beautiful in color. It is widely used in various fields.

However, in spite of the above excellent characteristics, it is not decomposed in the natural state and causes serious environmental pollution in the disposal of various products to which they are applied, and due to the depletion of fossil fuel, It is gradually decreasing or restricting. First of all, some products are prohibited from import and export, and it is urgent to develop materials that can replace synthetic resins due to the price increase of synthetic resin raw materials due to high oil prices.

As a material to replace the polymer synthetic resin produced by using fossil fuel having the above problems, there is a biodegradable synthetic resin using various grains which can be easily obtained from the surrounding, polylactic acid (PLA), polyglycolic acid (poly glycolic acid, PGA), poly caprolactone (PCL), aliphatic polyester resin, poly hydroxy butyric acid (PHB) or D-3-hydroxy butyl acid (D-3- Various biodegradable resins such as hydroxy butyric acid have been developed.

On the other hand, due to dimensional stability, weather resistance, chemical resistance, surface gloss, scratch resistance, ease of processing, various sheets such as marking sheets, interior sheets, decoration sheets, signboards, interior decoration sheets, etc. are used a lot.

However, the various sheets described above are made of synthetic resins having various problems, and recently, the use of eco-friendly materials is in the spotlight as environmental pollution problems arise.

In particular, the vinyl chloride sheet used in many applications releases a large amount of dioxins upon incineration. Such dioxin is a class 1 carcinogen that can be inherited by the World Health Organization (WHO) in 1992, and is classified as a reliable environmental hormone by the World Wildlife Fund (wwf). Produced as chemical contaminants in the process and occurs when burning compounds containing chlorine. These dioxins are chemically stable and do not break down naturally because they are not easily broken down or combined with other substances.They do not dissolve well in water, so they do not escape well in urine or feces. It is a colorless carcinogen that accumulates continuously in the animal's adipose tissue, and even if a small amount is ingested, has a toxic effect of 10,000 times of cyanide and 1,000 times of saccharin.

Therefore, sheets using starch or rubber, acrylic resins, alcoholic silanes, inorganic polymers, sheets using EPS (Expanded Polystyrene), polyvinyl butyral resins, polyvinyl acetal resins, PETG (Glycol-modified PET: Copolyesters) ), Poly Butylene Terephthalate (PBT), Acrylonitrile Butadiene Styrene (ABS), Liquid Crystalline Polymer (LCP), Dimethylnaphthalene (DMN), Polyoxymethylene (POM), Polymethylmetacrylate (PMMA), Polyphenylene Oxide (PPO), Polyphenylene Ether (PPE), Sheets using PAR (Polyarylate), PEEK (Polyehteretherketone), etc. are used, but recently, polylactic acid (PLA), hyaluronic acid (HA), polyhydroxybutyric acid (PHB), polyhydroxy valerate (PHV), polyvinyl alcohol (PVA), PHA (Polyhydroxyalkanoate), Polyhydroxyoctanoate (Polyhydroxyoctanoate), Polyethylene succinate, Polybutylene succinate, Polybutylene adipate, Sheets made of biodegradable resins such as polybutylene carbonate, polycaprolactone, polytetramethylene adipate, polytetramethylene terephthalate, polyethylene terephthalate, etc. It is widely used for environmental pollution prevention, waste disposal problem, light weight, strength and economy.

However, biodegradable synthetic resins, such as polylactic acid, polyglycolic acid, polycaprolactone, aliphatic polyester resins, polyhydroxybutyl acid or D-3-hydroxy butyric acid, have poor toughness and elongation, and are poor in adhesion and embossed. Machining is not easy, the embossed formed also tends to be lost or damaged, and there are many cracks.

On the other hand, the decoration sheet is used to form a variety of patterns on the surface to enhance the aesthetics, but when the portion to which the decoration sheet is bonded is an angled corner, the sheet is cut or easily damaged to obtain a satisfactory effect. The sheet used for the corner portion is thicker than the sheet used for the flat portion, but when the sheet itself is to be formed thickly, it is not easy to form the sheet. Therefore, two or more thin sheets are used for lamination. .

However, biodegradable synthetic resins such as polylactic acid, polyglycolic acid, polycaprolactone, aliphatic polyester resins, polyhydroxybutyl acid or D-3-hydroxy butyric acid are poor in toughness and elongation, and poor in adhesiveness, resulting in poor adhesion. There was a disadvantage that is not easily made.

Accordingly, it is an object of the present invention to provide a method for simultaneously laminating and embossing a biodegradable resin sheet, in which formed embossing is not lost or damaged, cracks are not generated, solvent resistance is excellent, and lamination and embossing are easy. have.

In order to achieve the above object as well as other objects that are easily expressed in the present invention, polylactic acid (PLA), polyglycolic acid (poly glycolic acid, PGA), polycaprolactone (poly caprolactone (PCL), aliphatic poly Biodegradable resin sheet mainly containing ester resin, poly hydroxy butyric acid (PHB) or D-3-hydroxy butyric acid, and acrylic resin sheet or the biodegradable A biodegradable resin sheet of the same type as the resin sheet is passed through a drum roller, and the surface temperature of the drum roller is 40 to 150 ° C., and the sheet is passed through the upper heater with radiant heat of 40 to 100 ° C., and the other biodegradable resin is passed through. A mixture of 5 to 40% by weight of aziridine was added based on the weight of the aqueous ink excluding the known pigment on the sheet. The sheet is embossed by passing it through the embossed sheet, but the temperature of the emboss is 50-150 ° C., the pressure of the emboss is 20-60 kgf / cm 2 and the temperature of the front heater is 80-200 ° C. Not only the lamination between the resin sheets was easily performed, but also the embossing formed was not lost or damaged, and lamination and embossing could be easily performed without cracking.

Simultaneous processing of lamination and embossing of the biodegradable resin sheet according to the present invention has no effect of losing or damaging the formed emboss, no cracking, excellent solvent resistance, and easy lamination and embossing. .

Simultaneous processing of lamination and embossing of the biodegradable resin sheet according to the present invention includes polylactic acid, polyglycolic acid, polycaprolactone, aliphatic polyester resin, polyhydroxybutyl acid or D-3-hydroxybutyl acid as main materials. The biodegradable resin sheet 1, the acrylic resin sheet 2, or the biodegradable resin sheet 1 'of the same type as the biodegradable resin sheet 1' are passed through the drum roller 10, and the surface temperature of the drum roller 10 is increased. It is made into 40-150 degreeC, it is made to pass through the upper heater 11, radiating heat of 40-100 degreeC, it laminates, and it is aziri with respect to the weight of the aqueous ink in which the well-known pigment was removed on the other biodegradable resin sheet 1 ". 5-40% by weight of azidedine was added, and the mixed mixture was coated with a primer layer of a matte coating, and then embossed by passing through the embossed sheet 13 together with the laminated sheet. Temperature is 50 ~ 150 ℃, emboss Pressure temperature of 20 ~ 60㎏f / ㎠, the front heater (12) (13) is characterized by performing a radiation condition of 80 ~ 200 ℃.

The biodegradable resin used in the present invention is one or two selected from the group consisting of polylactic acid, polyglycolic acid, polycaprolactone, aliphatic polyester resin, polyhydroxybutyl acid and D-3-hydroxy butyl acid. It is especially preferable when using a mixture of the above and using a polylactic acid.

Polylactic acid has a tensile modulus of elasticity similar to that of polyethylene terephthalate (PET), a general-purpose plastic resin, has excellent bending rigidity, and has a melting point of 171 ° C, which is higher than other biodegradable resins, but has an impact strength. It is low and easily absorbs moisture from the air and oxidizes quickly.

In the present invention, in order to solve the disadvantage of poor toughness, elongation and adhesion of the biodegradable resin used, forming a primer layer and embossing and laminating at the same time, the biodegradable resin sheet and the biodegradable resin sheet or biodegradable resin sheet And acrylic resin sheets are first laminated at specific temperature conditions, and the embossing produced by laminating the biodegradable resin sheets having the primer layer formed thereon is not lost or damaged, cracks are formed, and the lamination is easily performed. It was.

That is, using an acrylic resin sheet excellent in adhesion with a resin selected from the group consisting of polylactic acid, polyglycolic acid, polycaprolactone, aliphatic polyester resin, polyhydroxybutyl acid and D-3-hydroxybutyl acid. To perform the lamination or the biodegradable resin sheets to each other, but at a temperature condition that the adhesion is excellent, so that the lamination is made easily, and by forming a primer layer on one biodegradable resin sheet to facilitate lamination and embossing It was.

First, the biodegradable resin sheet 1 and the acrylic resin sheet 2 or the biodegradable resin sheet 1 'of the same kind as the biodegradable resin sheet 1' are passed through the drum roller 10, but the surface of the drum roller 10 The temperature is set to 40 to 150 ° C, and the upper heater 11 is allowed to pass through while applying radiant heat of 40 to 100 ° C for lamination. In this case, when the surface temperature of the drum roller and the temperature of the upper heater deviate from the above ranges, the lamination may not be easily performed, such that peeling may occur or bubbles may be formed.

Separately, a primer layer is formed on the surface of the biodegradable resin sheet 1 '. That is, a mixture of 5 to 40% by weight of aziridine is added to the weight of the aqueous ink without the pigment component in the known aqueous ink, and the mixed mixture is applied as a primer layer. In the present invention, the aqueous ink may be any known aqueous ink value, and may be used, except for pigments, among the main components consisting of aqueous resin dispersions, pigments, and water, and if necessary, other anti-foaming agents, surface modifiers, emulsifiers, Plasticizers and dispersants can also be used.

Aziridine is a colorless, flammable liquid with ammonia odor, chemical formula (CH ₂ ) ₂ NH, molecular weight 43.1, melting point -78 ℃, boiling point 55 ~ 56 ℃, soluble in water and organic solvents, secondary amine It is characterized by its unstable three-membered ring structure, which makes the ring open and reactive. Obtained by making potassium hydroxide act on (beta) -bromine ethylamine.

In the present invention, aziridine reacts with functional groups of biodegradable resins such as polylactic acid, polyglycolic acid, polycaprolactone, aliphatic polyester resin, polyhydroxybutyl acid or D-3-hydroxybutyl acid, Elongation is enhanced to make embossing easier, as well as to prevent loss of or damage to the formed emboss, and to prevent cracking.

In the present invention, it is preferable that 5 to 40% by weight of aziridine is added based on the weight of the aqueous ink, and when the addition amount is less than 5% by weight, the addition effect is weak and there is a disadvantage in that the embossing is not satisfactory, and 40% by weight. When it exceeds%, there is a problem in that there is no synergistic effect of addition, which is not economical, and deteriorates the biodegradable resin, thereby lowering the durability of the sheet.

Application of the primer layer in the present invention may use a coating method commonly used in the art to which the present invention belongs, for example, a coating method such as spin coating, inkjet printing, roll printing, dip coating, etc., wherein the primer layer is formed of at least one sheet of sheet paper. It is effective to carry out with a thickness of 0.05 to 0.2 mm on one surface, and when the thickness of the coating layer is less than 0.05 mm, the degree of expression of the coating effect is weak and the embossing is not satisfactory, and when the thickness exceeds 0.2 mm, it is an advantage as a biodegradable resin sheet. This has the disadvantage of deteriorating.

After forming the primer layer as described above, the biodegradable resin sheet (1), the acrylic resin sheet (2) or the biodegradable resin sheet (1 ') of the same type as the biodegradable resin sheet and the primer layer The formed biodegradable resin sheet 1 "is passed through together with the embossing 13 to carry out paper and embossing at the same time. The temperature of the embossing 13 is 50 to 150 캜 and the pressure of the embossing 13 to 20 kg. The temperature of f / cm <2> and the front heater 12 is performed on 80-200 degreeC radiant heat conditions.

In the present invention, when passing through the drum roller 10 as in the embossing process in the embossing process, the coated aziridine is inactivated, so that the embossing effect is not expressed.

If the temperature and pressure of the emboss 13 and the temperature of the front heater 12 is out of the above range there is a disadvantage that the emboss is not formed or the sheet of the biodegradable resin deteriorates.

The following examples illustrate the invention in more detail, but do not limit the invention.

Example  One

The polylactic acid was heated to 190 ° C. and melted, and then extruded at 190 ° C. and 70 kg / cm 2 using a twin-screw extruder to prepare a sheet having an average thickness of 0.2 mm.

Example  2

Water-based ink without pigment in the sheet prepared in Example 1 (KKW Co., Ltd. product name KCW: The main component is mainly based on a resin obtained by copolymerizing cellulose derivatives and unsaturated caprolactone intermediate polyols with acrylates) HMDI (hexamethylene diisocyanate) trimer and TDI Adduct type with excellent crosslinking agent with good resistance to blocking, and aziridine-containing mixture of 20% by weight of aqueous ink are coated by dip coating method. A mm thick primer layer is formed.

Separately, the sheet prepared in Example 1 and the acrylic resin sheet are laminated at the surface temperature of the drum roller 10 by 95 ° C., while passing through the drum roller 10 while applying radiant heat of 70 ° C. to the upper heater 11. .

Then, the laminated sheet and the sheet on which the primer layer is formed are passed through the emboss while maintaining the temperature of the embossing temperature of 100 ° C., the embossing pressure of 40 kgf / cm 2, and the front heater temperature of 140 ° C. to simultaneously carry out the lamination and embossing. It was done.

After laminating and embossing the sheet was placed in a dry oven and maintained at 100 ° C. for 60 minutes, the embossing was visually observed to show that the sheet was not damaged, and no interlaminar peeling or bubble formation could be confirmed. The sheet was again maintained for 60 minutes in the freezing chamber at minus 10 ℃, 60 minutes in a dry oven at 100 ℃, the visual observation of the embossing was confirmed that there was no damage, the lamination state did not change.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic schematic diagram of the embossing process method of the biodegradable resin sheet which concerns on this invention.

* Explanation of symbols for the main parts of the drawings

1. Biodegradable resin sheet 10. Drum roller

11. Upper Heater 12. Front Heater

13. Emboss 14. Rubber Roller

15. Guide roller

Claims (1)

Biodegradable resin sheet (1) mainly containing polylactic acid, polyglycolic acid, polycaprolactone, aliphatic polyester resin, polyhydroxybutyl acid or D-3-hydroxy butyl acid, and acrylic resin sheet (2) or The biodegradable resin sheet 1 'of the same kind as the biodegradable resin sheet 1' is passed through the drum roller 10, and the surface temperature of the drum roller 10 is 40 to 150 DEG C, and the upper heater 11 is 40 to 100. The mixture was laminated while passing through radiant heat at &lt; RTI ID = 0.0 &gt; C, &lt; / RTI &gt; and mixed by adding 5 to 40% by weight of aziridine with respect to the weight of the aqueous ink excluding a known pigment on another biodegradable resin sheet 1 ". After coating with a primer layer of a matte coating, and then embossed by passing through the laminated sheet together with the emboss 13, the temperature of the emboss 13 is 50 ~ 150 ℃, the pressure of the emboss 13 20 ~ 60 kgf / cm 2, the temperature of the front heater 12 is 80 ~ 200 ℃ radiant heat Laminating and embossing the same time the processing method of the biodegradable resin sheet, characterized in that for performing cases.

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