KR20130104435A - Biodegradable molding product and biodegradable film including thereof - Google Patents

Abstract

PURPOSE: A biodegradation molding material is provided to facilitate discard by biodegrading and to have no material property degradation of water resistance, oil resistance, and strength by containing a mineral filler or a plant filler. CONSTITUTION: A biodegradation molding material comprises 5-1000 parts by weight of mineral filler and/or 6-200 parts by weight of plant filler based on 100 parts by weight of aliphatic polyester. The aliphatic polyester is selected from polylactic acid, polycaprolactone, polyhydroxy butylate, polybutylene succinate, and polybutylene terephthalate. The mineral filler is selected from talc, carbonate, silica, and titanium oxide. Moreover, the biodegradation film comprises a core(100) including the biodegradation molding material and a printing layer(200) formed on the top of the core.

Description

Biodegradable molding material and biodegradable film comprising the same {BIODEGRADABLE MOLDING PRODUCT AND BIODEGRADABLE FILM INCLUDING THEREOF}

The present invention relates to a biodegradable molding material and a biodegradable film comprising the same. More particularly, the present invention relates to a biodegradable molding material and a biodegradable film comprising the aliphatic polyester and at least one of a mineral filler or a vegetable filler.

At present, as a molding material, a laminate of printed and printed films on PVC and MDF materials is used. However, the molding material as described above has a problem in that it must be incinerated at the time of disposal after use by using polyvinyl chloride (PVC) and melamine resin. In addition, the Republic of Korea Patent Publication No. 10-2005-0107250 discloses an environmentally friendly PVC composition while including the chaff in the PVC resin composition, having the properties of PVC resin having excellent physical properties such as water resistance and chemical resistance, but It does not describe the composition etc. which are biodegradable and easy to dispose.

Of course, researches on biodegradable resins decomposed by microorganisms present in soil and photodegradable resins decomposed by ultraviolet light of solar light are still being conducted, but the manufacturing cost is still high. Various problems such as the complete decomposition are not solved.

In order to solve the above problems, an object of the present invention is to achieve a complete decomposition that the conventional biodegradable resin did not have, an environmentally friendly molding material and biodegradable film comprising the biodegradable is easy to dispose To provide that purpose.

In order to achieve the above object, the present invention is a biodegradable molding material comprising at least one of mineral filler 5 to 1000 parts by weight and vegetable filler 5 to 200 parts by weight with respect to 100 parts by weight of aliphatic polyester to provide.

In order to achieve another object of the present invention, there is provided a biodegradable film comprising a core and a printing layer on the core including the molding material.

The biodegradable molding material according to the present invention is completely decomposed, and has an excellent effect in ease of disposal, and there is no deterioration in physical properties such as water resistance, oil resistance and strength due to the inclusion of an optical filler or a vegetable filler. In addition, the molding is excellent and the manufacturing cost is low.

In addition, by including the core and the print layer comprising the bio-degradable molding material, it is possible to give the interior characteristics peculiar to the molding material, and to maintain continuously.

1 and 2 show a cross section of a biodegradable film composed of a core and a print layer comprising the biodegradable molding material of the present invention.
3 and 4 show a cross-sectional view of a biodegradable film composed of a core print layer comprising a biodegradable molding material of the present invention.

Advantages and features of the present invention, and methods for achieving them will be apparent with reference to the following embodiments. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

Hereinafter, the present invention will be described in detail.

Biodegradable Molding material

The present invention contains a mineral filler or a vegetable filler in the aliphatic polyester to produce a biodegradable molding material. More specifically, the biodegradable molding material of the present invention is characterized by including at least one of 5 to 1000 parts by weight of mineral filler or 5 to 200 parts by weight of vegetable filler with respect to 100 parts by weight of aliphatic polyester.

The aliphatic polyester has high biodegradability, polylactic acid, polycaprolactone, polyhydroxybutyrate polybutylenesuccinate, and polybutylene terephthalate terephtalate) may include one or two or more selected from among the aliphatic polyesters, the higher the amount of the aliphatic polyester, the better the processability and the lower the heat deflection temperature. It is preferable to add.

In this case, the aliphatic polyester resin is preferably polylactic acid in view of high heat resistance of 150 ° C. and high rigidity. The polylactic acid is a polymer of a low molecular weight compound present in the living body such as lactic acid as a representative material of a biodegradable polymer or biodegradable plastic. In general, polylactic acid is used for milling renewable resources such as corn to separate starch from raw materials and to process crude glucose from the starch. The glucose is made into lactic acid through the fermentation process, the lactic acid becomes polylactide through the condensation process. The polylactide disintegrates and lowers the plastic material by the action of the enzymes secreted by the microorganisms, and then the microorganisms absorb these low molecules to metabolize them, finally producing microbial cells, carbon dioxide, methane gas and the like and finally decomposing them.

The mineral filler contained in the biodegradable molding material of the present invention is characterized by including 5 to 1000 parts by weight of the mineral filler with respect to 100 parts by weight of the aliphatic polyester. When the mineral filler is included in less than 5 parts by weight, it is difficult to achieve the original purpose of economic production, and when included in excess of 1000 parts by weight, there is a problem that the mechanical strength is reduced to form a molding material. In particular, the mineral filler is preferably included in 150 to 800 parts by weight, because it is easy to economically produce molding material and excellent mechanical strength by maintaining the content.

In addition, the mineral filler of the present invention may include one or two or more selected from talc, calcium carbonate (coal), silica and titanium oxide as applied to produce more economically. The mineral filler is used for the purpose of lowering the cost of the entire composition, or controlling the hardness or strength, and when the content exceeds a certain amount, the processability and physical properties of the molding material are lowered, and when the content is less than the content, the shape stability of the molded product is deteriorated.

Among the mineral fillers, it is preferable to include talc, since the talc is used in various ways due to its properties such as strong absorption and sticking property and fire resistance when powdered. In particular, it exhibits excellent heat resistance, good mixing properties with other resins, and strong dimensional fixation force after fixing, which is more preferable to compensate for rigidity and strength.

The particle diameter of the said mineral filler can be 5-40 micrometers. If the particle diameter of the mineral filler is less than 5 μm, it is difficult to disperse and the strength is lowered. If the particle size of the mineral filler exceeds 40 μm, the particle size becomes too large and the surface becomes rough.

The present invention includes vegetable fillers including corn-related materials, starch-producible materials, and other natural materials. More specifically, the vegetable filler is one or two selected from corn starch, potato starch, sweet potato starch, wheat starch, tapioca starch, rice starch, wood powder, wood powder, natural cellulose fiber, polyvinyl alcohol fiber, chitosan and cellulose acetate. It may include more than one species. In addition, other natural materials may further include pine needles, rice straw, vines, sawdust, rice husks, leaves and thinning products.

The starch-producible material is abundant in nature, easy to obtain, and is the cheapest and most environmentally friendly material. Therefore, the more it is used, the more competitive in price, but if the content exceeds a certain level, the processability and physical properties of the composition are rapidly lowered. When the content of the starch is less than a certain level, the amount of aliphatic polyester used is relatively increased and thus the economical efficiency is lowered. The starch may be any type of starch obtained from cereals, but corn starch, potato starch, and sweet potato starch are more preferable in that it is easily obtained.

The vegetable filler included in the biodegradable molding material of the present invention may include 5 to 200 parts by weight based on 100 parts by weight of the aliphatic polyester, and more preferably 15 to 100 parts by weight. When the content of the vegetable filler is less than 5 parts by weight, there is a problem in that the production price is increased without being excellent in processability and other physical properties. When the content of the vegetable filler is more than 200 parts by weight, the density of the vegetable filler is lower than that of the inorganic filler. There is a problem that the mechanical strength is significantly lowered due to the characteristics.

In addition, when the biodegradable molding material of the present invention includes 5 to 1000 parts by weight of the mineral filler and 5 to 200 parts by weight of the vegetable filler with respect to 100 parts by weight of the aliphatic polyester, to achieve complete decomposition that the conventional biodegradable resin did not have, It can be commercialized due to its low price. In addition, by maintaining the content of the mineral filler and vegetable filler to a certain range, it is possible to increase the processability and durability of the biodegradable molding material. For the same reason as above, it is preferable to include aliphatic polyester, a range of mineral fillers and vegetable fillers together.

The biodegradable molding material composition of the present invention may include 0.1 to 5 parts by weight of an additive with respect to 100 parts by weight of the aliphatic polyester in order to improve the bonding strength between the aliphatic polyester and the mineral filler and the vegetable filler. When the additive is included in less than 0.1 part by weight, there is a concern that the increase in bonding strength is insignificant, and when the amount exceeds 5 parts by weight, the production price is increased without improving the bonding strength.

The additive that can be used in the present invention may include at least one of a compound containing two or more epoxy groups or an acrylic resin.

Compounds containing two or more of these epoxy groups chemically react with aliphatic polyesters and with hydroxyl groups present in mineral fillers and vegetable fillers to improve mechanical strength.

In addition, any compound containing two or more epoxy groups used in the present invention may have an average of two or more epoxy groups per molecule. Preferably it has 2 to 50 epoxy groups, more preferably 2 to 20 epoxy groups. Such compounds include polymers or oligomers having epoxy groups called so-called epoxy resins. The epoxy group may be any structure having an oxirane ring structure, and may represent, for example, glycidyl group, oxyethylene group, epoxycyclohexyl group, and the like.

More specifically, Polyglycidyl ether obtained by making epichlorohydrin react with polyhydric phenols, such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol, or polyhydric alcohols, such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; Polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; And epoxidized phenol novolac resins, epoxidized cresol novolac resins, epoxidized polyolefins, cycloaliphatic epoxy resins, other urethane-modified epoxy resins, and the like, but are not limited thereto.

By using the compound containing two or more of the epoxy groups as the additive of the present invention, the bonding strength between the resin and the filler is improved to improve the melt strength during processing, thereby improving the overall workability and excellent effect on improving the mechanical strength of the molding.

The acrylic resin included as the additive is also because the acrylic resin improves mechanical strength by improving entanglement between the resin and the filler by the long molecular form. More specifically, the acrylic resin is methyl methacrylate, urethane acrylate, epoxy acrylate, silicone acrylate, ethylhexyl acrylate, butyl acrylate, ethyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, glyc Cydyl methacrylate, glycidyl acrylate, behenyl acrylate, ethyl acrylate, lauryl acrylate, stearyl acrylate, acrylic acid, hydroxy ethyl acrylate, hydroxy butyl acrylate, hydroxy ethyl methacryl All acrylics having one or more double bonds in the molecular structure, such as acrylate, phenoxy acrylate, methyl acrylate, hexanediol diacrylate, can be used, and can be used by polymerizing or polymerizing a polymer. Mixing in monomer form Used, or the polymerization and the polymer can be used in combination with a solvent, if having a transparency which does not hinder the visibility of the display device as an acrylic resin may be suitably selected.

In particular, the molecular weight of the acrylic resin in the present invention is preferably from 600,000 to 5 million g / mol, more preferably from 1 to 3 million g / mol in terms of mechanical strength improvement. . If the molecular weight of the acrylic resin is less than 600,000 g / mol as the molecular weight is small, there is a possibility that the intermolecular entanglement is small, and the effect of improving the mechanical strength is insignificant, and when the acrylic resin exceeds 5 million g / mol and other resins due to high melting temperature Kneading is a difficult problem.

The biodegradable molding material of the present invention may contain other known additives as long as the object of the present invention is not impaired. Examples of the other known additives include plasticizers, reinforcing agents, inorganic or glass fillers, antioxidants, heat stabilizers, ultraviolet absorbers, and other lubricants, waxes, colorants, crystallization accelerators, organic substances having degradability such as starch, and the like. . These may be used alone or in combination of a plurality thereof.

Biodegradable film

The present invention provides a biodegradable film comprising a core including the biodegradable molding material and a print layer on the core.

The biodegradable molding material comprising at least one of mineral fillers 5 to 1000 parts by weight and vegetable fillers 5 to 200 parts by weight with respect to 100 parts by weight of the aliphatic polyester of the present invention can be molded by a known molding method. . The biodegradable molding material is as described above.

For example, film molding, extrusion molding, injection molding, etc. are mentioned, Extrusion molding is especially preferable among these. More specifically, extrusion molding can be performed according to a conventional method, for example using well-known extrusion molding machines, such as a single extruder and a twin extruder. In addition, injection molding can be carried out in a known injection molding machine such as an in-line screen injection molding machine, a multilayer injection molding machine, a bilateral injection molding machine or the like according to the conventional method.

Referring to FIG. 1, the molding material is formed to show a biodegradable film including a print layer 200 on an upper portion of the core 100 to impart interior properties to the extruded core 100.

The print layer 200 may be formed by plywood on the core, the print layer 200 may be made of paper, synthetic resin, etc., in particular, it is possible to use a film made of paper, aliphatic polyester resin is biodegradable It is more preferable at the point. In this case, the paper may be one impregnated with a resin.

The print layer of the present invention may include an aliphatic polyester, a mineral filler, and the like to form a white sheet having a core-like property through calendering, and to form a print layer on the white sheet by gravure printing. In addition, the thickness of the printed layer is not particularly limited without departing from the object of the present invention.

Referring to FIG. 2, the surface treatment layer 300 may be further included on the printed layer 200. The surface treatment layer 300 is for antifouling treatment, and shows an excellent effect on scratch resistance and stain resistance, and is preferably formed using a microgravure coating.

In addition, the coating thickness of the surface treatment agent 300 of the surface treatment layer 300 is preferably 1 to 200 μm, but is not limited thereto. The surface treatment agent may be a urethane isocyanate di-component treatment agent or a urethane one-component treatment agent. It may be coated with natural drying or hot air drying, or a surface treating agent of a urethane acrylate or epoxy acrylate-based coating may be coated on the printed layer by UV curing.

According to the method of manufacturing a biodegradable film of the present invention, the core 100 and the print layer 200 may form a film using heat or an adhesive, including an adhesive layer 110 between the core and the print layer. can do.

The adhesive layer 110 serves to attach the core 100 and the print layer 200, and the components may include acrylic, urethane, vinyl acetate, and the like. At this time, the thickness of the adhesive layer is not particularly limited within the range of achieving the object for preventing the core 100 and the printed layer 200 from peeling off. By heating and compressing the core 100 and the print layer 200, the biodegradable film may be manufactured, and thus the object of the present invention may be achieved without including the adhesive layer 110.

Referring to FIG. 3, the biodegradable film of the present invention may include a core printing layer 400 having two or more colors and patterns by injecting two or more colors of pigments and resin mixtures into an extruder die proximal. have. The core print layer 400 may impart interior properties to the core itself, and may have decorative and interior effects even if it does not include a separate print layer.

Therefore, the biodegradable film of the present invention may not include a core and a print layer, respectively, and may include a core print layer 400, wherein the core and the print layer are formed of one layer.

Even when the biodegradable film of the present invention includes the core print layer 400, the surface treatment layer 300 may be separately formed on the core print layer 400 as shown in FIG.

At this time, the surface treatment layer 300 is also for the antifouling treatment, by using a urethane acrylate can exhibit an excellent effect on scratch resistance and stain resistance, using a micro gravure coating core printed layer 400 It can be formed by applying to the top.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. . Accordingly, the true scope of the present invention should be determined by the following claims.

Example 1

500 parts by weight of charcoal (calcium carbonate) and 5 parts by weight of plasticizer Acetyl Tributyl Citrate (ATBC) were kneaded in Kneader at 160 ° C based on 100 parts by weight of PLA resin (2003D) to prepare a composition. The prepared composition was extruded into a bar shape having a width of 10 mm * 70 mm at 140 ° C in a single extruder to cut a length of 1500 mm to form a core layer.

100 parts by weight of PLA resin (2003D), 80 parts by weight of charcoal (calcium carbonate), 10 parts by weight of TiO _2, 10 parts by weight of plasticizer acetyltributyl citrate (ATBC), white sheet through calendering process Formed.

A printed pattern was formed by printing a wood pattern on the formed white sheet by a gravure printing method. The prepared core layer and the printed layer were heat-compressed two layers at 80 ° C. to form a biodegradable film.

Example 2

30 parts by weight of wood powder and 100 parts by weight of PLA resin (2003D) and 5 parts by weight of plasticizer acetyltributyl citrate (ATBC) were kneaded at Kneader at 160 ° C. to prepare a composition. The prepared composition was extruded into a bar shape having a width of 10 mm * 70 mm at 140 ° C in a single extruder to cut a length of 1500 mm to form a core layer.

The white sheet of Example 1 was printed with a wooden pattern by a gravure printing method to coat an acrylic treatment agent to form a printed layer with a surface treatment layer. The biodegradable film was formed by thermally compressing the printed layer having the core layer and the surface treatment layer attached thereto at 80 ° C.

Example 3

500 parts by weight of talc (calcium carbonate), 30 parts by weight of wood powder and 5 parts by weight of a plasticizer acetyl tributyl citrate (ATBC) were kneaded in a Kneader at 160 DEG C per 100 parts by weight of PLA resin (2003D) . The prepared composition was extruded into a bar shape having a width of 10 mm * 70 mm at 140 ° C in a single extruder to cut a length of 1500 mm to form a core layer.

80 parts by weight of charcoal (calcium carbonate), 100 parts by weight of PLA resin (2003D), TiO ₂ 10 parts by weight of acetyltributyl citrate (ATBC) to form a white sheet through a calendering process at a composition ratio of 10 parts by weight.

A printed pattern was formed by printing a wood pattern on the formed white sheet by a gravure printing method. A biodegradable film was formed using an adhesive including a urethane resin between the prepared core layer and the print layer.

Comparative Example 1

After the core layer was made of synthetic wood (MDF) material, a PVC-printed film was bonded using vinyl acetate resin to form a biodegradable film.

Comparative Example 2

With respect to 100 parts by weight of the PLA resin (2003D), a biodegradable film was formed in the same manner as in Example 3 except that the carbonite (calcium carbonate) was included 1500 parts by weight and 250 parts by weight of wood powder. However, the resin bonding strength and the mechanical strength were insufficient to form the bar.

< Experimental Example > -Biodegradable Molding material  Biodegradation Measurement

Biodegradation experiments were carried out with the biodegradable molding materials forming the core layers of Examples 1 to 3 and Comparative Examples 1 and 2, but the experiments were conducted according to the guidelines of KS M3100-1: 2003, but virtual aerobic composting was performed. The biodegradability was measured by the ratio of the theoretical carbon dioxide generation and the actual carbon dioxide generation from the test substance. At this time, the test environment was incubated in a dark place with a temperature of 58 ± 2 ℃, humidity of about 50% and no gas that could inhibit the activity of microorganisms.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Biodegradability 98% 92% 96% 0% Molding impossible

Biodegradation (%) experimented by the above method is shown in Table 1. The biodegradability of Example 1 containing a certain amount of mineral filler (coal) and Example 2 containing a certain amount of vegetable filler (wood powder) showed an experimental result of 90% or more. In addition, the biodegradable molding material containing a range of mineral fillers and vegetable fillers showed a biodegradability of almost 100%, and the biodegradable molding material of Example 3 was found to be very environmentally friendly.

On the other hand, the biodegradability of the biodegradable molding material included in the film formed by printing with a conventional MDF material was 0%, which revealed a conventional problem that there is no environmentally friendly property. In contrast, in the case of the biodegradable molding material of Comparative Example 2 including a mineral filler and a vegetable filler that deviates from a certain range, the biodegradable molding material has a low mechanical strength due to the content of a small resin. I couldn't.

100: core
110: adhesive layer
200: printed layer
300: surface treatment layer
400: core print layer

Claims (11)

A biodegradable molding material comprising at least one of 5 to 1000 parts by weight of mineral filler and 5 to 200 parts by weight of vegetable filler with respect to 100 parts by weight of aliphatic polyester.
The method of claim 1,
The aliphatic polyester is biodegradable molding material, characterized in that one or two or more selected from polylactic acid, polycaprolactone, polyhydroxy butyrate, polybutylene succinate and polybutylene terephthalate.
The method of claim 1,
The mineral filler is biodegradable molding material, characterized in that one or two or more selected from talc, calcium carbonate, silica and titanium oxide.
The method of claim 1,
The mineral filler is a biodegradable molding material, characterized in that the particle size of 5 ~ 40㎛.
The method of claim 1,
The vegetable filler is one or two or more selected from corn starch, potato starch, sweet potato starch, wheat starch, tapioca starch, rice starch, wood powder, wood powder, natural cellulose fiber, polyvinyl alcohol fiber, chitosan and cellulose acetate. Biodegradable molding material.
The method of claim 1,
Of the biodegradable molding material
A biodegradable molding material comprising 0.1 to 5 parts by weight of an additive based on 100 parts by weight of the aliphatic polyester.
The method according to claim 6,
The additive is a biodegradable molding material characterized in that it comprises a compound or an acrylic resin containing two or more epoxy groups.
8. The method of claim 7,
Biodegradable molding material characterized in that the molecular weight of the acrylic resin is 600,000 to 5 million g / mol.
The method of claim 1,
A biodegradable film comprising a core comprising the biodegradable molding material and a printed layer on the core.
The method of claim 9,
Biodegradable film, characterized in that the core and the printed layer consists of one layer.
11. The method according to claim 9 or 10,
Biodegradable film, characterized in that it further comprises a surface treatment layer on the printed layer.

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