WO2017131364A1 - Eggshell powder resin composition - Google Patents

Eggshell powder resin composition Download PDF

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Publication number
WO2017131364A1
WO2017131364A1 PCT/KR2017/000361 KR2017000361W WO2017131364A1 WO 2017131364 A1 WO2017131364 A1 WO 2017131364A1 KR 2017000361 W KR2017000361 W KR 2017000361W WO 2017131364 A1 WO2017131364 A1 WO 2017131364A1
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Prior art keywords
resin composition
eggshell powder
present
weight
parts
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PCT/KR2017/000361
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French (fr)
Korean (ko)
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이형진
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주식회사 에코원
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Priority to JP2018530596A priority Critical patent/JP2019503411A/en
Priority to CN201780008505.4A priority patent/CN108602977A/en
Publication of WO2017131364A1 publication Critical patent/WO2017131364A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to an eggshell powder resin composition, and more particularly, it is possible to reduce the cost by recycling the eggshell powder, which is a food waste, and to prepare a molded article having a smooth surface appearance with excellent dispersibility between the eggshell powder and the base resin. It is related with the eggshell powder resin composition which can be used.
  • Patent Documents KR2013-0068620A, KR2014-0094865A and the like have a method of producing powders obtained by pulverizing plants or herbal agricultural wastes, and then blending them with plastic resins to produce molded articles such as injection and extrusion. Is disclosed.
  • the disclosed materials or methods are biomass-added plastic materials, which have the advantage of being biodegradable when disposed of in landfills.
  • the present inventors have completed the present invention by focusing on finding a material capable of reducing the cost while reducing the amount of carbon dioxide generated when incinerated and disposed of.
  • It is an object of the present invention to provide a resin composition comprising an eggshell powder capable of producing a molded article having a cost-saving and smooth surface appearance.
  • Another object of the present invention is to provide a molded article produced from the resin composition.
  • Eggshell powder resin composition according to the present invention for achieving the above object, with respect to 100 parts by weight of a polymer polymer; Eggshell powder 5 to 50 parts by weight; characterized in that it comprises a.
  • the polymer is preferably capable of melt kneading with an egg shell powder at a temperature of 200 ° C. or less.
  • the egg shell powder is preferably size that passes through a 100 mesh sieve (opening ⁇ 150 ⁇ m).
  • the eggshell powder resin composition may further include 10 to 30 parts by weight of the inorganic filler based on 100 parts by weight of the polymer polymer.
  • the eggshell powder may further include 1 to 10 parts by weight of wax based on 100 parts by weight of the polymer polymer.
  • the resin composition according to the present invention is an environmentally friendly material, it is possible to reduce the cost by recycling the eggshell which is food waste and using it as a plastic material.
  • the resin composition according to the present invention is a material that is added to reduce the cost, as a non-combustible material is added to the biomass, the amount of carbon dioxide generated during the incineration waste is less environmental burden.
  • the resin composition according to the present invention is excellent in the dispersion of the egg shell powder and the base resin, it can be produced into a molded article having a smooth appearance.
  • FIG. 1 is a photograph of an injection molded article manufactured using an eggshell powder resin composition according to an embodiment of the present invention.
  • Figure 2 is a photograph of the injection molded article produced using the eggshell powder resin composition according to a comparative example.
  • Eggshell powder resin composition according to the invention is characterized in that it comprises 5 to 50 parts by weight of eggshell powder with respect to 100 parts by weight of the polymer polymer.
  • the polymer polymer to be applied to the eggshell powder resin composition of the present invention a polymer material known in the art that is applied to food packaging materials, baby products, bathroom products, kitchen products, etc. may be used.
  • a polymer material capable of kneading processing in a molten state with an egg shell powder at a temperature of 200 ° C. or lower, more preferably 190 ° C. or lower is used.
  • the temperature exceeds 200 ° C discoloration occurs due to the carbonization of the egg shell, and an unpleasant odor occurs during the kneading processing. After the work was completed, it was found to remain for a considerable time. Described as the non-limiting intention, it is understood that the generation of discoloration and odor is caused by carbonization of a protein contained in a small amount in eggshell.
  • the resin which can be applied as the base resin to the eggshell powder resin composition of the present invention is a resin having a melting point of 190 ° C or lower.
  • Non-limiting intentions include, for example, polyethylene including linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE); Ethylene vinyl acetate (EVA); Polyvinyl alcohol (PVA); And polypropylene (PP) homopolymers or copolymers of propylene and C3-C10 alkenes; ABS; Nylon, polyester; And the like can be applied as the base resin to the composition of the present invention.
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • EVA Ethylene vinyl acetate
  • PVA Polyvinyl alcohol
  • PP polypropylene
  • Eggshell powder to be applied to the present invention is a finely pulverized eggshell (shell) of algae, reptiles and powdered.
  • the collected egg shells are manufactured through a series of operations including washing, removing egg shell membranes, drying, grinding, and the like.
  • calcium carbonate is composed mainly of carbonate ( ⁇ 93wt%), small amount of magnesium carbonate ( ⁇ 1wt%), calcium phosphate ( ⁇ 1wt%), and proteins ( ⁇ 5wt%).
  • the egg shell powder can be obtained commercially in the form of a powder in a state that is ground to various sizes.
  • Eggshell powder applied to the present invention is preferably 100 mesh sieve (opening ⁇ 150 ⁇ m), more preferably 200 mesh sieve (opening ⁇ 70 ⁇ m), most preferably 400 mesh sieve (opening ⁇ 40 ⁇ m) Use a size that passes through. According to the inventors' repetition experiment, it was confirmed that the dispersion of the base resin and the egg shell powder was not desired in the case of the size not passing through the 100 mesh sieve.
  • the content of the eggshell powder in the composition according to the present invention is preferably 5 to 50 parts by weight of eggshell powder based on 100 parts by weight of the polymer polymer.
  • the content of the eggshell powder exceeds 50 parts by weight, the physical properties of the base resin material (for example, tensile strength, elongation, impact strength, etc.) are severely reduced.
  • an inorganic filler may be further included.
  • the inorganic filler used for this purpose may be any one or more of calcium carbonate, clay, ocher, talc and kaolin. Most preferably calcium carbonate is used.
  • the content of the inorganic filler is preferably used 5 parts by weight to 30 parts by weight based on 100 parts by weight of the polymer.
  • the inorganic filler is used at less than 5 parts by weight, the kneading and dispersion are not sufficiently improved.
  • more than 30 parts by weight is used, deterioration of physical properties such as strength, tensile strength and elongation of the product is caused.
  • wax may be added to the eggshell powder resin composition according to the present invention.
  • the wax is coated on the surface of the eggshell powder to improve the dispersion of the eggshell powder and the base resin, and also serves to prevent water absorption of the eggshell powder.
  • the wax used for this purpose can be applied to the composition of the present invention without limitation if it is commercially available, for example, paraffin wax, liquid paraffin wax, beeswax, drive wax, emulsion wax, candelilla wax, PE Waxes, PP waxes and the like can be used.
  • the usage-amount of the said wax is 1-20 weight part with respect to 100 weight part of high polymers.
  • the function of coating and lubricant is weak, and when it is used more than 20 parts by weight, the excess amount may be eluted in the manufacturing and post-process of the composition, which may cause surface defects and poor workability (elution of foreign substances). have.
  • the wax may be added to the composition by mixing the base resin and egg shell powder, inorganic fillers and other additives, and then extruding.
  • Another example of the eggshell powder input is that the wax is premixed with the eggshell powder to be used in the form of an eggshell powder coated with wax.
  • the surface-coated eggshell powder can be obtained by injecting wax into the eggshell powder and stirring the mixture at high speed at 300 to 800 rpm while dissolving the wax by self-heating during stirring to coat the surface of the eggshell powder.
  • composition according to the present invention may further include additives known in the art, such as a heat stabilizer, an antioxidant, a lubricant, a mold release agent, a nucleating agent, a pigment, a dye, a UV stabilizer, a flame retardant, and a plasticizer, as necessary.
  • additives known in the art such as a heat stabilizer, an antioxidant, a lubricant, a mold release agent, a nucleating agent, a pigment, a dye, a UV stabilizer, a flame retardant, and a plasticizer, as necessary.
  • the eggshell powder resin composition according to the present invention may be prepared by a known method of melt kneading the components and then pelletizing them.
  • melt kneading of the composition may be carried out using a single screw extruder or twin screw extruder, and the addition of each component of the composition may be carried out by hand blending or crushing the base resin, egg shell powder, inorganic filler and other necessary additives in powder or pellet form.
  • Compounding may be carried out using a suitable means such as a vari mixer and then introduced into the extruder, or some components may be added to other locations of the extruder while weighing. After melt kneading is complete, it can be pelletized and used in the next process.
  • the eggshell powder resin composition according to the present invention was prepared in a composition according to the mixing ratio according to the following Table 1.
  • an egg shell powder and wax were added to a high speed stirrer, and a high speed stirring was performed at a speed of 400 rpm to prepare an egg shell powder coated with wax.
  • the polypropylene resin, the prepared wax-coated eggshell powder, calcium carbonate, and Zn-stearate are blended and then put into a hopper of a twin screw extruder, melt kneaded at a maximum temperature of 190 ° C. in a barrel, and then cooled, Cut to prepare a composition in pellet state.
  • thermoplastic resin compositions of Examples and Comparative Examples prepared above By using the thermoplastic resin compositions of Examples and Comparative Examples prepared above, the product in the form of egg seat was injection molded.
  • FIG. 1 is a photograph of an injection molded article manufactured using a composition according to an embodiment of the present invention
  • FIG. 2 is a photograph of an injection molded article manufactured using a composition according to a comparative example.
  • the dispersion of the egg shell powder is uniform and thus, a molded article having a smooth surface state can be obtained.
  • Figure 2 in the case of using only the base resin and eggshell powder in preparing the eggshell powder resin composition, it was confirmed with the naked eye that the dispersion state of the eggshell powder in the final molded product using the composition. From the above results, it was confirmed that when preparing an eggshell powder resin composition, an inorganic filler (particularly, calcium carbonate) should be additionally added so that the eggshell powder dispersion state is good and a product having a uniform thickness can be produced. .
  • an inorganic filler particularly, calcium carbonate
  • the eggshell powder resin composition according to the present invention may be applied to a food packaging material, a baby article, a bathroom article, a kitchen utensil, an automobile interior, an industrial article, and the like by a known molding method such as injection molding, extrusion molding or sheet molding.

Abstract

The present invention provides a resin composition containing 5-50 parts by weight of an eggshell powder relative to 100 parts by weight of a polymer. The resin composition according to the present invention, which is an eco-friendly material, can be cost-reduced by recycling eggshells, which correspond to a food waste, to be used as a plastic material. In addition, the resin composition according to the present invention has a low environmental burden since the amount of carbon dioxide generated during incineration disposal is small as a non-combustible material instead of the biomass is added as a material that is added for cost reduction. Further, the resin composition according to the present invention has excellent dispersibility with an eggshell powder and a base resin, and thus can be manufactured into a molded article with a good appearance.

Description

난각분말 수지 조성물Eggshell Powder Resin Composition
본 발명은 난각분말 수지 조성물에 관한 것으로, 보다 상세하게는 식품폐기물인 난각분말을 재활용하여 원가절감이 가능하면서도, 난각분말과 기초수지와의 분산성이 우수하여 유려한 표면 외관을 갖는 성형품의 제조가 가능한 난각분말 수지 조성물에 관한 것이다.The present invention relates to an eggshell powder resin composition, and more particularly, it is possible to reduce the cost by recycling the eggshell powder, which is a food waste, and to prepare a molded article having a smooth surface appearance with excellent dispersibility between the eggshell powder and the base resin. It is related with the eggshell powder resin composition which can be used.
근래에 들어 식품 포장재로 이용되는 필름을 포함한 각종 플라스틱 사용량의 증가에 따라, 소재/제품의 개발시 그 폐기방법까지 고려하여 환경부담이 작으면서도 원가절감까지 가능한 소재의의 개발이 다양한 방법으로 시도되고 있다.In recent years, with the increase in the amount of various plastics including films used as food packaging materials, the development of materials that can reduce costs and reduce costs is considered in various ways considering the disposal method when developing materials / products. have.
예를 들어, 특허문헌 KR2013-0068620A, KR2014-0094865A 등에는 식물체를 분쇄하여 수득한 분말이나, 초본계 농산폐기물을 분말화한 다음 이를 플라스틱 수지와 배합하여 사출, 압출 등의 성형품으로 제조하는 방법이 개시되어 있다. 개시된 소재나 방법들은 바이오 매스가 첨가된 플라스틱 소재들로서, 매립하여 폐기하는 경우 생분해가 가능하다는 이점이 있다.For example, Patent Documents KR2013-0068620A, KR2014-0094865A and the like have a method of producing powders obtained by pulverizing plants or herbal agricultural wastes, and then blending them with plastic resins to produce molded articles such as injection and extrusion. Is disclosed. The disclosed materials or methods are biomass-added plastic materials, which have the advantage of being biodegradable when disposed of in landfills.
그러나, 상술한 바이오 매스 첨가 소재들은 플라스틱 소재와 상용성이 좋지 않은 것이 보통이므로, 이를 플라스틱 소재와 배합/혼련하기 위하여는 전처리에 상당한비용이 투입되어야 하고, 또한, 매립하여 폐기하는 경우에는 생분해성을 갖는다는 점이 유리하기는 하나, 소각하여 폐기하는 경우에는 바이오 매스도 결국에는 이산화탄소의 형태로 환경으로 돌아간다는 점에서, 종래의 플라스틱 소재와 환경에 주는 부담이 다르지 않다.However, since the above-mentioned biomass-added materials are generally not compatible with plastic materials, a considerable cost must be put into pretreatment in order to mix / mix them with plastic materials, and biodegradability in the case of landfill disposal Although it is advantageous to have, the burden on the environment is not different from the conventional plastic material in that in case of incineration and disposal, the biomass eventually returns to the environment in the form of carbon dioxide.
이에, 본 발명자들은 소각하여 폐기하는 경우 이산화탄소의 발생량이 적으면서도 원가절감이 가능한 소재를 찾기 위해 노력한 결과, 식품폐기물인 난각을 플라스틱 소재의 충진제로 적용할 수 있음에 착안하여 본 발명을 완성하였다.Accordingly, the present inventors have completed the present invention by focusing on finding a material capable of reducing the cost while reducing the amount of carbon dioxide generated when incinerated and disposed of.
본 발명의 목적은, 원가절감이 가능하면서도 유려한 표면 외관을 갖는 성형품의 제조가 가능한 난각분말을 포함하는 수지 조성물을 제공하는 것이다.It is an object of the present invention to provide a resin composition comprising an eggshell powder capable of producing a molded article having a cost-saving and smooth surface appearance.
본 발명의 다른 목적은, 상기 수지 조성물로부터 제조되는 성형품을 제공하는 것이다.Another object of the present invention is to provide a molded article produced from the resin composition.
상기 목적을 달성하기 위한 본 발명에 따르는 난각분말 수지 조성물은, 고분자 중합체 100중량부에 대하여; 난각분말 5 내지 50중량부;를 포함하는 것을 특징으로 한다.Eggshell powder resin composition according to the present invention for achieving the above object, with respect to 100 parts by weight of a polymer polymer; Eggshell powder 5 to 50 parts by weight; characterized in that it comprises a.
상기 고분자 중합체는 200℃ 이하의 온도에서 난각분말과 용융 혼련이 가능한 것임이 바람직하다.The polymer is preferably capable of melt kneading with an egg shell powder at a temperature of 200 ° C. or less.
상기 난각분말은 100메쉬 체(개구 ~150㎛)를 통과하는 크기인 것이 바람작하다.The egg shell powder is preferably size that passes through a 100 mesh sieve (opening ~ 150㎛).
상기 난각분말 수지 조성물은 고분자 중합체 100 중량부에 대하여 무기 필러 10 내지 30중량부를 추가로 포함할 수 있다.The eggshell powder resin composition may further include 10 to 30 parts by weight of the inorganic filler based on 100 parts by weight of the polymer polymer.
상기 난각분말 고분자 중합체 100중량부에 대하여 왁스 1 내지 10중량부를 추가로 포함할 수 있다.The eggshell powder may further include 1 to 10 parts by weight of wax based on 100 parts by weight of the polymer polymer.
본 발명에 따르는 수지 조성물은 친환경적인 소재로서, 식품폐기물인 난각을 재활용하여 플라스틱의 소재로 사용하여 원가절감이 가능하다. As the resin composition according to the present invention is an environmentally friendly material, it is possible to reduce the cost by recycling the eggshell which is food waste and using it as a plastic material.
또한 본 발명에 따르는 수지 조성물은 원가절감을 위하여 투입되는 재료로서 바이오 매스가 아니라 불연성의 재료를 투입함에 따라, 소각폐기시에 이산화탄소의 발생량이 적어 환경부담이 적다.In addition, the resin composition according to the present invention is a material that is added to reduce the cost, as a non-combustible material is added to the biomass, the amount of carbon dioxide generated during the incineration waste is less environmental burden.
또한, 본 발명에 따르는 수지 조성물은 난각분말과 기초수지와의 분산이 우수하여, 유려한 외관을 갖는 성형품으로 제조될 수 있다.In addition, the resin composition according to the present invention is excellent in the dispersion of the egg shell powder and the base resin, it can be produced into a molded article having a smooth appearance.
도 1은 본 발명의 실시예에 따르는 난각분말 수지 조성물을 이용하여 제작된 사출성형품에 대한 사진이고,1 is a photograph of an injection molded article manufactured using an eggshell powder resin composition according to an embodiment of the present invention.
도 2는 비교예에 따르는 난각분말 수지 조성물을 이용하여 제작된 사출성형품에 대한 사진이다.Figure 2 is a photograph of the injection molded article produced using the eggshell powder resin composition according to a comparative example.
본 발명에 따르는 난각분말 수지 조성물은 고분자 중합체 100중량부에 대하여 난각분말 5 내지 50중량부를 포함하는 것을 특징으로 한다.Eggshell powder resin composition according to the invention is characterized in that it comprises 5 to 50 parts by weight of eggshell powder with respect to 100 parts by weight of the polymer polymer.
본 발명의 난각분말 수지 조성물에 적용되는 고분자 중합체는, 식품포장재, 유아용품, 욕실용품, 주방용품 등으로 적용되는 당업계 공지의 고분자 재료가 사용될 수 있다.As the polymer polymer to be applied to the eggshell powder resin composition of the present invention, a polymer material known in the art that is applied to food packaging materials, baby products, bathroom products, kitchen products, etc. may be used.
바람직하게는, 200℃ 이하의 온도에서, 보다 바람직하게는 190℃ 이하의 온도에서 난각분말과 융해 상태에서 혼련가공이 가능한 고분자 재료를 적용한다. 발명자들의 반복실험에 따르면, 난각분말과 고분자 재료의 혼련가공에 있어 온도가 200℃를 초과하는 경우에는 난각의 탄화로 인하여 변색이 발생하고, 또한, 혼련가공 중 불쾌한 냄새가 발생하며, 이러한 냄새는 작업이 완료된 후에도 상당기간 잔존하는 것으로 확인되었다. 상기 비한정적인 의도로서 설명하자면, 상기 변색과 냄새의 발생은 난각에 소량으로 포함된 단백질의 탄화에 의하여 발생하는 것으로 이해된다.Preferably, a polymer material capable of kneading processing in a molten state with an egg shell powder at a temperature of 200 ° C. or lower, more preferably 190 ° C. or lower is used. According to the inventors' repeated experiments, in the kneading processing of the eggshell powder and the polymer material, when the temperature exceeds 200 ° C, discoloration occurs due to the carbonization of the egg shell, and an unpleasant odor occurs during the kneading processing. After the work was completed, it was found to remain for a considerable time. Described as the non-limiting intention, it is understood that the generation of discoloration and odor is caused by carbonization of a protein contained in a small amount in eggshell.
통상적으로, 고분자 수지 가공온도의 하한은 융점보다 10℃ 높은 온도 정도이다. 따라서, 본 발명의 난각분말 수지 조성물에 기초수지로 적용될 수 있는 수지는 190℃ 이하의 융점을 갖는 수지이다. 비제한적인 의도로서 예를 들자면, 선형저밀도폴리에틸렌(LLDPE), 저밀도폴리에틸렌(LDPE), 고밀도폴리에틸렌(HDPE)을 포함하는 폴리에틸렌; 에틸렌비닐아세테이트(EVA); 폴리비닐알코올(PVA); 및 폴리프로필렌(PP) 단독중합체나, 프로필렌과 C3~C10의 알켄의 공중합체; ABS; 나일론, 폴리에스테르; 등이 본 발명의 조성물에 기초 수지로 적용될 수 있다.Usually, the lower limit of the polymer resin processing temperature is about 10 ° C higher than the melting point. Therefore, the resin which can be applied as the base resin to the eggshell powder resin composition of the present invention is a resin having a melting point of 190 ° C or lower. Non-limiting intentions include, for example, polyethylene including linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE); Ethylene vinyl acetate (EVA); Polyvinyl alcohol (PVA); And polypropylene (PP) homopolymers or copolymers of propylene and C3-C10 alkenes; ABS; Nylon, polyester; And the like can be applied as the base resin to the composition of the present invention.
본 발명에 적용되는 난각분말은 조류, 파충류 동물의 난각(알껍질)을 미세하게 분쇄하여 분말화 한 것이다. 통상적으로는, 수거된 난각을 세정, 난각막 제거, 건조, 분쇄 등을 포함하는 일련의 작업을 거쳐 제조된다. 조성적으로는 탄산칼슘이 주성분을 이루고(~93wt%), 소량의 탄산마그네슘(~1wt%), 인산칼슘(~1wt%), 단백질류(~5wt%)를 포함하는 것으로 알려져 있다.Eggshell powder to be applied to the present invention is a finely pulverized eggshell (shell) of algae, reptiles and powdered. Typically, the collected egg shells are manufactured through a series of operations including washing, removing egg shell membranes, drying, grinding, and the like. It is known that calcium carbonate is composed mainly of carbonate (~ 93wt%), small amount of magnesium carbonate (~ 1wt%), calcium phosphate (~ 1wt%), and proteins (~ 5wt%).
상기 난각분말은 다양한 크기로 분쇄된 상태의 분말상태로 상업적으로 입수될 수 있다. 본 발명에 적용되는 난각분말은, 바람직하게는 100메쉬 체(개구 ~150㎛), 더욱 바람직하게는 200메쉬의 체(개구 ~70㎛), 가장 바람직하게는 400메쉬 체(개구 ~40㎛)를 통과하는 크기의 것을 사용한다. 발명자들의 반복실험에 따르면, 100메쉬의 체를 통과하지 못하는 크기인 경우에는 기초수지와 난각분말의 분산이 원할하지 않은 것으로 확인되었다.The egg shell powder can be obtained commercially in the form of a powder in a state that is ground to various sizes. Eggshell powder applied to the present invention is preferably 100 mesh sieve (opening ~ 150㎛), more preferably 200 mesh sieve (opening ~ 70㎛), most preferably 400 mesh sieve (opening ~ 40㎛) Use a size that passes through. According to the inventors' repetition experiment, it was confirmed that the dispersion of the base resin and the egg shell powder was not desired in the case of the size not passing through the 100 mesh sieve.
한편, 본 발명에 따르는 조성물에서 난각분말의 함량은 고분자 중합체 100중량부에 대하여 난각분말 5 내지 50중량부인 것이 바람직하다. 난각분말의 함량이 50중량부를 초과하는 경우에는 기초 수지 소재의 물성(예를 들어, 인장강도, 신율, 충격강도 등)의 저하가 심하게 된다.On the other hand, the content of the eggshell powder in the composition according to the present invention is preferably 5 to 50 parts by weight of eggshell powder based on 100 parts by weight of the polymer polymer. When the content of the eggshell powder exceeds 50 parts by weight, the physical properties of the base resin material (for example, tensile strength, elongation, impact strength, etc.) are severely reduced.
본 발명에 따르는 조성물에는, 바람직하게는 무기 필러가 더 포함될 수 있다. 역시 발명자들의 반복실험에 따르면, 무기 필러가 추가로 포함되는 경우 그 작용의 기작은 명확치 않으나 난각분말과 기초 수지의 혼련 및 분산이 개선되는 것으로 확인되었다. 이 목적으로 사용되는 무기 필러는 탄산칼슘, 점토, 황토, 활석 및 카오린 중 어느 하나 이상일 수 있다. 가장 바람직하게는 탄산칼슘을 사용한다.In the composition according to the present invention, preferably an inorganic filler may be further included. Also, according to the inventors' repeated experiments, when the inorganic filler is additionally included, the mechanism of the action is not clear, but it was confirmed that the kneading and dispersion of the eggshell powder and the base resin are improved. The inorganic filler used for this purpose may be any one or more of calcium carbonate, clay, ocher, talc and kaolin. Most preferably calcium carbonate is used.
한편, 무기 필러의 함량은 상기 고분자 중합체 100중량부에 대하여 5 중량부 내지 30중량부를 사용하는 것이 좋다. 무기 필러를 5중량부 미만으로 사용하는 경우 혼련 및 분산이 개선이 충분치 않고, 한편, 30중량부 이상 사용시에는 제품의 강도 인장 강도, 연신율 등 물성의 저하가 유발된다.On the other hand, the content of the inorganic filler is preferably used 5 parts by weight to 30 parts by weight based on 100 parts by weight of the polymer. When the inorganic filler is used at less than 5 parts by weight, the kneading and dispersion are not sufficiently improved. On the other hand, when more than 30 parts by weight is used, deterioration of physical properties such as strength, tensile strength and elongation of the product is caused.
또한, 본 발명에 따르는 난각분말 수지 조성물에는 왁스가 첨가될 수 있다. 상기 왁스는 난각분말의 표면에 코팅되어 난각분말과 기초수지의 분산을 개선하고, 또한, 난각분말의 수분흡수 방지하는 기능을 한다. 이 목적으로 사용되는 왁스는 상업적으로 구입이 가능한 것이라면 제한 없이 본 발명의 조성물에 적용될 수 있어, 예를 들어, 파라핀 왁스, 유동 파라핀 왁스, 밀납, 몰다 왁스, 이멀시파잉 왁스, 칸데릴라 왁스, PE 왁스, PP 왁스 등이 사용될 수 있다.In addition, wax may be added to the eggshell powder resin composition according to the present invention. The wax is coated on the surface of the eggshell powder to improve the dispersion of the eggshell powder and the base resin, and also serves to prevent water absorption of the eggshell powder. The wax used for this purpose can be applied to the composition of the present invention without limitation if it is commercially available, for example, paraffin wax, liquid paraffin wax, beeswax, drive wax, emulsion wax, candelilla wax, PE Waxes, PP waxes and the like can be used.
상기 왁스의 사용량은 고분자 중합체 100 중량부에 대하여 1 내지 20중량부의 비율인 것이 바람직하다. 1중량부 미만으로 사용시 코팅기능 및 활제 보조제 역할이 미약하고, 20중량부를 초과하여 사용하는 경우 초과량이 조성물의 제조 및 후공정에서 용출되어 표면불량 및 작업성 불량(이물질 용출)의 원인이 될 수 있다.It is preferable that the usage-amount of the said wax is 1-20 weight part with respect to 100 weight part of high polymers. When it is used less than 1 part by weight, the function of coating and lubricant is weak, and when it is used more than 20 parts by weight, the excess amount may be eluted in the manufacturing and post-process of the composition, which may cause surface defects and poor workability (elution of foreign substances). have.
상기 왁스는 기초수지와 난각분말, 무기 필러 기타 첨가제 등을 혼합한 다음, 압출하는 방법으로 조성물에 투입될 수 있다. 난각분말 투입의 다른 예는, 상기 왁스가 난각분말과 사전 배합되어 왁스가 표면 코팅된 난각분말의 형태로 사용되는 것이다. 표면 코팅된 난각분말은, 난각분말에 왁스를 투입하고 300 내지 800rpm으로 고속 교반시키면서, 교반시 발생하는 자가발열에 의하여 왁스를 용해시켜 난각분말의 표면을 코팅하는 방법으로 얻을 수 있다.The wax may be added to the composition by mixing the base resin and egg shell powder, inorganic fillers and other additives, and then extruding. Another example of the eggshell powder input is that the wax is premixed with the eggshell powder to be used in the form of an eggshell powder coated with wax. The surface-coated eggshell powder can be obtained by injecting wax into the eggshell powder and stirring the mixture at high speed at 300 to 800 rpm while dissolving the wax by self-heating during stirring to coat the surface of the eggshell powder.
한편, 본 발명에 따른 조성물에는 필요에 따라 열안정제, 산화방지제, 활제, 이형제, 핵제, 안료, 염료, 자외선안정제, 난연제, 가소제 등 당업계 공지의 첨가제들이 추가로 포함될 수 있음은 물론이다.Meanwhile, the composition according to the present invention may further include additives known in the art, such as a heat stabilizer, an antioxidant, a lubricant, a mold release agent, a nucleating agent, a pigment, a dye, a UV stabilizer, a flame retardant, and a plasticizer, as necessary.
본 발명에 따르는 난각분말 수지 조성물은 구성성분을 용융 혼련한 다음, 이를 펠렛화하는 공지의 방법으로 제조될 수 있다.The eggshell powder resin composition according to the present invention may be prepared by a known method of melt kneading the components and then pelletizing them.
예를 들어, 조성물의 용융 혼련은 일축 압출기나 이축 압출기를 이용하여 수행될 수 있으며, 조성물 각 성분의 투입은 파우더나 펠렛 상태의 기초수지, 난각분말, 무기 필러 및 기타 필요한 첨가제를 핸드 블렌딩이나 반바리 믹서 등 적당한 수단을 이용하여 배합한 다음 압출기에 투입되거나, 또는 일부 성분은 계량하면서 압출기의 다른 위치에 투입될 수도 있다. 용융 혼련이 완료된 다음에는 이를 펠렛화하여 다음 공정에 사용될 수 있다.For example, melt kneading of the composition may be carried out using a single screw extruder or twin screw extruder, and the addition of each component of the composition may be carried out by hand blending or crushing the base resin, egg shell powder, inorganic filler and other necessary additives in powder or pellet form. Compounding may be carried out using a suitable means such as a vari mixer and then introduced into the extruder, or some components may be added to other locations of the extruder while weighing. After melt kneading is complete, it can be pelletized and used in the next process.
이하, 실시예를 통하여 본 발명의 구성 및 그에 따른 효과를 보다 상세히 설명한다. 본 실시예는 본 발명을 보다 구체적으로 설명하기 위한 예시일 뿐이며, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.Hereinafter, the configuration of the present invention and its effects through the following examples will be described in more detail. This embodiment is only an illustration for explaining the present invention more specifically, the scope of the present invention is not limited to these examples.
다음의 표 1에 따르는 배합비율에 따르는 조성으로 본 발명에 따르는 난각분말 수지 조성물을 준비하였다.The eggshell powder resin composition according to the present invention was prepared in a composition according to the mixing ratio according to the following Table 1.
Figure PCTKR2017000361-appb-T000001
Figure PCTKR2017000361-appb-T000001
먼저, 고속 교반기에 난각분말과 왁스를 투입하고, 400rpm의 속도로 고속 교반하여 표면에 왁스가 코팅된 난각분말을 준비하였다. 다음으로, 폴리프로필렌 수지, 상기 준비된 왁스 코팅된 난각분말, 탄산칼슘, 및 Zn-스테아레이트를 배합한 다음, 이축압출기의 호퍼에 투입하고, 배럴의 최고온도 190℃에서 용융 혼련시킨 후, 냉각, 컷팅하여 펠렛 상태의 조성물을 제조하였다.First, an egg shell powder and wax were added to a high speed stirrer, and a high speed stirring was performed at a speed of 400 rpm to prepare an egg shell powder coated with wax. Next, the polypropylene resin, the prepared wax-coated eggshell powder, calcium carbonate, and Zn-stearate are blended and then put into a hopper of a twin screw extruder, melt kneaded at a maximum temperature of 190 ° C. in a barrel, and then cooled, Cut to prepare a composition in pellet state.
상기 제조된 실시예와 비교예의 열가소성 수지조성물을 이용하여, 난좌 형태의 제품을 사출성형 하였다.By using the thermoplastic resin compositions of Examples and Comparative Examples prepared above, the product in the form of egg seat was injection molded.
도 1은 본 발명의 실시예에 따르는 조성물을 이용하여 제작된 사출성형품에 대한 사진이고 도 2는 비교예에 따르는 조성물을 이용하여 제작된 사출성형품에 대한 사진이다. 도 1을 참조할 때, 고분자 중합체와 난각분말을 용융 혼련함에 있어, 무기 필러를 함께 사용하는 경우 난각분말의 분산이 균일하여 표면상태가 유려한 성형품을 얻을 수 있음을 확인할 수 있다. 반면, 도 2로부터, 난각분말 수지 조성물을 제조함에 있어 기초 수지와 난각분말 만을 사용하는 경우, 조성물을 사용하여 최종 성형된 제품에서 난각분말의 분산상태가 불균일함을 육안으로 확인할 수 있었다. 상기 결과로부터, 난각분말 수지 조성물을 제조함에 있어, 무기 필러(특히, 탄산칼슘)을 추가로 투입하여야, 난각분말의 분산상태가 양호하고, 또한, 균일한 두께의 제품을 제작할 수 있음을 확인하였다.1 is a photograph of an injection molded article manufactured using a composition according to an embodiment of the present invention, and FIG. 2 is a photograph of an injection molded article manufactured using a composition according to a comparative example. Referring to FIG. 1, in melt kneading a polymer polymer and an egg shell powder, when an inorganic filler is used together, the dispersion of the egg shell powder is uniform and thus, a molded article having a smooth surface state can be obtained. On the other hand, from Figure 2, in the case of using only the base resin and eggshell powder in preparing the eggshell powder resin composition, it was confirmed with the naked eye that the dispersion state of the eggshell powder in the final molded product using the composition. From the above results, it was confirmed that when preparing an eggshell powder resin composition, an inorganic filler (particularly, calcium carbonate) should be additionally added so that the eggshell powder dispersion state is good and a product having a uniform thickness can be produced. .
본 발명에 따르는 난각분말 수지 조성물은 사출성형, 압출성형 또는 시트성형 등의 공지의 성형방법으로 방법으로, 식품포장재, 유아용품, 욕실용품, 주방용품, 자동차 내장재, 산업용품 등에 적용될 수 있다.The eggshell powder resin composition according to the present invention may be applied to a food packaging material, a baby article, a bathroom article, a kitchen utensil, an automobile interior, an industrial article, and the like by a known molding method such as injection molding, extrusion molding or sheet molding.

Claims (4)

  1. 고분자 중합체 100중량부에 대하여 난각분말 5 내지 50중량부, 무기 필러 10 내지 30중량부 및 왁스 1 내지 10중량부를 포함하는 난각분말 수지 조성물.An egg shell powder resin composition comprising 5 to 50 parts by weight of an egg shell powder, 10 to 30 parts by weight of an inorganic filler, and 1 to 10 parts by weight of a wax, based on 100 parts by weight of the polymer.
  2. 제1항에 있어서, 상기 고분자 중합체는 200℃ 이하의 온도에서 난각분말과 용융 혼련이 가능한 것임을 특징으로 하는 난각분말 수지 조성물.The egg shell powder resin composition of claim 1, wherein the polymer polymer is capable of melt kneading with the egg shell powder at a temperature of 200 ° C or lower.
  3. 제1항에 있어서, 상기 난각분말은 100메쉬 체(개구 ~150㎛)를 통과하는 크기인 것을 특징으로 하는 난각분말 수지 조성물.The egg shell powder composition of claim 1, wherein the egg shell powder has a size that passes through a 100 mesh sieve (opening-150 µm).
  4. 제1항 내지 제3항중 어느 한 항의 수지 조성물로부터 제조되는 성형품.The molded article manufactured from the resin composition of any one of Claims 1-3.
PCT/KR2017/000361 2016-01-27 2017-01-11 Eggshell powder resin composition WO2017131364A1 (en)

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