KR20230009639A - Method for manufacturing masterbatch for greenhouse film having ability of thermal blocking - Google Patents
Method for manufacturing masterbatch for greenhouse film having ability of thermal blocking Download PDFInfo
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- KR20230009639A KR20230009639A KR1020210090306A KR20210090306A KR20230009639A KR 20230009639 A KR20230009639 A KR 20230009639A KR 1020210090306 A KR1020210090306 A KR 1020210090306A KR 20210090306 A KR20210090306 A KR 20210090306A KR 20230009639 A KR20230009639 A KR 20230009639A
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- Prior art keywords
- greenhouse film
- metal
- metal powder
- greenhouse
- dispersing
- Prior art date
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- 230000000903 blocking effect Effects 0.000 title claims abstract description 38
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title abstract description 10
- 239000002184 metal Substances 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 45
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 17
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920006243 acrylic copolymer Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 5
- 229910006913 SnSb Inorganic materials 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 abstract description 8
- 230000000243 photosynthetic effect Effects 0.000 abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 239000011324 bead Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- PHEDXBVPIONUQT-RGYGYFBISA-N phorbol 13-acetate 12-myristate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(CO)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C PHEDXBVPIONUQT-RGYGYFBISA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
Abstract
Description
본 발명은 열차단능이 있는 온실 필름용 마스터배치의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a masterbatch for a greenhouse film having thermal barrier function.
일반적으로 비닐하우스는 비닐, 시트(필름) 등으로 제조한 온실을 의미한다. 비닐하우스는 원래 기온이 낮아 작물이 성장하기 어려운 동절기에 수확철이 지난 과일이나 야채 등이 성장할 수 있는 온실 환경을 조성하기 위하여 제조된 것이다. 그러나, 근래에 들어 비닐하우스의 4계절 활용도가 높아지면서, 겨울을 제외한 광량이 증가하는 계절에 비닐하우스의 온실 효과를 조정할 필요성이 대두되었다. 즉, 종래의 비닐하우스는 온실 효과를 극대화하기 위하여 제조되어, 겨울철을 제외하고는 비닐하우스 내부의 온도가 지나치게 높아져 농작물이 고사하는 문제가 발생하였는 바, 태양광으로 인한 온도 상승 효과 제어에 대한 니즈가 강하게 부각되었다. 한편, 이러한 문제점을 해결하기 위하여, 비닐하우스 외부에 태양광선의 유입을 막기 위한 별도의 막을 설치하는 시도가 있었으나, 이 경우 가시광선 유입을 지나치게 방해하여 작물의 생장을 저해하거나, 설치 및 관리가 용이하지 않다는 문제점이 있었다.In general, a vinyl house means a greenhouse made of vinyl, sheet (film), and the like. The vinyl house is originally manufactured to create a greenhouse environment in which fruits or vegetables that have passed the harvest season can grow during the winter season when the temperature is low and crops are difficult to grow. However, in recent years, as the utilization of the four seasons of the vinyl house has increased, the need to adjust the greenhouse effect of the vinyl house has emerged in the season when the amount of light increases except for winter. That is, the conventional vinyl house is manufactured to maximize the greenhouse effect, and the temperature inside the greenhouse becomes excessively high except in winter, causing crops to die. Need for controlling the temperature increase effect due to sunlight was strongly highlighted. On the other hand, in order to solve this problem, there has been an attempt to install a separate membrane to block the inflow of sunlight outside the greenhouse, but in this case, the inflow of visible light is excessively hindered, which hinders the growth of crops or is easy to install and manage. There was a problem with not doing it.
일 측면에서 본 발명의 목적은 열차단율이 우수한 필름을 제조하는 것이다.In one aspect, an object of the present invention is to manufacture a film having excellent thermal insulation rate.
일 측면에서 본 발명의 목적은 적외선 차단력이 우수한 필름을 제조하는 것이다.In one aspect, an object of the present invention is to manufacture a film having excellent infrared blocking power.
일 측면에서 본 발명의 목적은 가시광선 투과율은 유지하면서 적외선 차단력이 우수한 필름을 제조하는 것이다.In one aspect, an object of the present invention is to manufacture a film having excellent infrared ray blocking power while maintaining visible light transmittance.
일 측면에서 본 발명의 목적은 온실의 열차단에 최적화된 필름을 제조하는 것이다.In one aspect, an object of the present invention is to manufacture a film optimized for thermal insulation of a greenhouse.
일 측면에서 본 발명의 목적은 고온 환경에서 식물 생장에 필요한 광합성 파장은 통과하며, 뜨거운 적외선 차단율이 우수한 필름을 제조하는 것이다.In one aspect, an object of the present invention is to manufacture a film that passes the photosynthetic wavelength required for plant growth in a high temperature environment and has excellent hot infrared blocking rate.
상기 목적을 달성하기 위하여, 본 발명은 일 측면에서, 메틸에틸케톤, 프로필렌 글리콜 모노에틸 에테르, 및 프로필렌 글리콜 메틸 에테르로 구성된 군으로부터 선택된 유기용제 및 아민류를 포함하는 분산 보조제의 혼합물에 적외선 차단능을 갖는 금속을 분산시켜, 1차 분산액을 얻는 단계; 상기 1차 분산액을 포화지방산에 분산시켜, 2차 분산액을 얻는 단계; 상기 2차 분산액을 건조하여 금속 분말을 얻는 단계; 및 상기 금속 분말과 수지를 혼합하는 단계를 포함하는, 온실 필름용 마스터배치의 제조방법을 제공한다.In order to achieve the above object, in one aspect, the present invention provides a mixture of an organic solvent selected from the group consisting of methyl ethyl ketone, propylene glycol monoethyl ether, and propylene glycol methyl ether, and a dispersing aid containing amines, to have infrared blocking ability. dispersing the metal having to obtain a primary dispersion; dispersing the first dispersion in saturated fatty acid to obtain a second dispersion; drying the secondary dispersion to obtain metal powder; And it provides a method for producing a master batch for a greenhouse film, comprising mixing the metal powder and the resin.
본 발명의 일 측면인 온실 필름용 마스터배치의 제조방법에 의할 경우, 가시광선 투과율은 유지하면서, 원적외선, 중적외선 및 근적외선을 포함하는 넓은 범위의 적외선에 대한 차단율이 우수한 온실 필름을 제조할 수 있다. 또한, 상기 온실 필름은 식물 재배에 필수적인 광합성 파장은 투과시키며, 내부 온도 증가의 원인인 적외선은 차단하여 내부 온도를 연중 일정하게 유지할 수 있다. 따라서, 온실의 내부 온도 유지에 필요한 에너지를 절감할 수 있으며, 재배 기간을 늘릴수 있어 연평균 수확량을 늘릴 수 있다. 또한, 상기 마스터배치를 활용한 온실 필름의 경우, 고온(하절기)에서 더욱 우수한 적외선 차단율을 나타내어, 고온 환경에서도 온실의 과도한 온도 상승을 제어할 수 있다.According to the method for manufacturing a masterbatch for a greenhouse film, which is one aspect of the present invention, a greenhouse film having excellent blocking rate for a wide range of infrared rays including far infrared rays, mid infrared rays and near infrared rays can be manufactured while maintaining visible light transmittance. there is. In addition, the greenhouse film can maintain a constant internal temperature throughout the year by transmitting photosynthetic wavelengths essential for plant cultivation and blocking infrared rays that cause an increase in internal temperature. Therefore, it is possible to save energy required to maintain the internal temperature of the greenhouse, and it is possible to increase the annual average yield by extending the cultivation period. In addition, in the case of the greenhouse film using the masterbatch, it exhibits a more excellent infrared ray blocking rate at high temperature (summer season), so that excessive temperature rise in the greenhouse can be controlled even in a high temperature environment.
이하에서, 각 구성을 보다 상세히 설명하나, 이는 하나의 예시에 불과할 뿐, 본 발명의 권리범위가 다음 내용에 의해 제한되지 아니한다.Hereinafter, each configuration will be described in more detail, but this is only one example, and the scope of the present invention is not limited by the following content.
본 발명의 명세서 및 청구범위에 사용된 용어 또는 단어는 통상적이거나 사전적인 의미로 한정 해석되지 아니하며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. Terms or words used in the specification and claims of the present invention are not limited to the usual or dictionary meaning, and the inventor can properly define the concept of the term in order to explain his/her invention in the best way. Based on the principle, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.
본 발명의 명세서 전체에 있어서, 어떤 부분이 어떤 구성 요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.Throughout the specification of the present invention, when a part "includes" a certain component, it means that it may further include other components, not excluding other components unless otherwise stated. .
본 발명은 일 측면에서, 메틸에틸케톤((Methyl ethyl ketone, MEK), 프로필렌 글리콜 모노에틸 에테르(Propylene glycol mono ethyl ether, PM), 및 프로필렌 글리콜 메틸 에테르(Propylene glycol methyl ether, PMA)로 구성된 군으로부터 선택된 유기용제 및 아민류를 포함하는 분산 보조제의 혼합물에 적외선 차단능을 갖는 금속을 분산시켜, 1차 분산액을 얻는 단계; 상기 1차 분산액을 포화지방산에 분산시켜, 2차 분산액을 얻는 단계; 상기 2차 분산액을 건조하여 금속 분말을 얻는 단계; 및 상기 금속 분말과 수지를 혼합하는 단계를 포함하는, 온실 필름용 마스터배치의 제조방법이다.In one aspect, the present invention is a group consisting of methyl ethyl ketone (MEK), propylene glycol mono ethyl ether (PM), and propylene glycol methyl ether (PMA) Obtaining a first dispersion by dispersing a metal having infrared ray blocking ability in a mixture of an organic solvent selected from and a dispersing aid containing amines; Dispersing the first dispersion in saturated fatty acid to obtain a second dispersion; The above A method for preparing a masterbatch for a greenhouse film comprising the steps of drying the secondary dispersion to obtain metal powder and mixing the metal powder with a resin.
일 측면에서, 상기 유기 용제는 분산 보조제를 100 중량부로 할 때, 1000~2000 중량부, 또는 1300~2000 중량부, 또는 1300~1800 중량부로 포함될 수 있다.In one aspect, the organic solvent may be included in 1000 to 2000 parts by weight, or 1300 to 2000 parts by weight, or 1300 to 1800 parts by weight based on 100 parts by weight of the dispersion aid.
또한, 상기 금속 분말은, 분산 보조제를 100 중량부로 할 때, 100~1000 중량부, 또는 200~800 중량부, 또는 200~600 중량부로 포함될 수 있다.In addition, the metal powder may be included in an amount of 100 to 1000 parts by weight, 200 to 800 parts by weight, or 200 to 600 parts by weight, based on 100 parts by weight of the dispersion aid.
일 측면에서, 분산 보조제는, 금속 분말의 총 질량을 기준으로, 1~10중량%로 포함될 수 있다.In one aspect, the dispersion aid may be included in an amount of 1 to 10% by weight based on the total mass of the metal powder.
유기 용제, 금속 분말, 및 분산 보조제가 상기와 같은 함량으로 포함되지 않을 경우엔, 적외선 차단 효과가 저하되거나, 분산 안정성 및 저장성이 크게 저하되는 문제점이 발생할 수 있다.When the organic solvent, the metal powder, and the dispersing aid are not included in the above amounts, problems such as reduced infrared ray blocking effect or significantly reduced dispersion stability and storability may occur.
일 측면에서, 상기 분산 보조제는 아민류, 아민가 94 mg KOH/g, 산가 94 mg KOH/g, 및 밀도(20℃) 1.08 g/ml인 산기를 포함하는 알킬롤 암모늄 염(Alkylol ammonium salt of a copolymer with acidic groups), 및 아크릴계 공중합체 중 하나 이상을 포함할 수 있으며, 일 구현예에서, 상기 3종의 물질이 모두 포함될 수 있다. 3종의 물질이 모두 포함될 경우에, 상기 아민류는 상기 3종 물질 총 중량 100 중량%를 기준으로, 0.1~10 중량%, 또는 0.1~5 중량%, 또는 0.1~3 중량%, 또는 0.1~1 중량%로 포함될 수 있고, 알킬롤 암모늄 염과 아크릴계 공중합체는 각각 1: 0.8~1.2의 중량비, 또는 동량으로 포함될 수 있다.In one aspect, the dispersing aid is an amine, an amine value of 94 mg KOH / g, an acid value of 94 mg KOH / g, and an alkylol ammonium salt of a copolymer containing an acid group having a density (20 ° C.) of 1.08 g / ml. with acidic groups), and at least one of an acrylic copolymer, and in one embodiment, all three types of materials may be included. When all three types of materials are included, the amines are 0.1 to 10% by weight, or 0.1 to 5% by weight, or 0.1 to 3% by weight, or 0.1 to 1% by weight based on 100% by weight of the total weight of the three materials. It may be included in weight%, and the alkylol ammonium salt and the acrylic copolymer may be included in a weight ratio of 1: 0.8 to 1.2, or the same amount.
상기 방법은, 상기 1차 분산액을 얻는 단계 이후에 상기 분산액의 수분을 건조시키는 단계를 더 포함할 수 있다. The method may further include drying moisture of the dispersion after obtaining the first dispersion.
또한, 일 측면에서 상기 방법은 상기 1차 분산액의 수분을 건조시키는 단계 이후에, 분쇄하는 단계를 더 포함할 수 있다.In addition, in one aspect, the method may further include a step of grinding after drying the moisture of the first dispersion.
상기 분쇄는 밀링(milling)을 포함할 수 있으며, 일 측면에서, 상기 밀링은 금속 비드를 이용하여 수행하는 것을 포함할 수 있다.The grinding may include milling, and in one aspect, the milling may include performing using a metal bead.
일 측면에서, 상기 금속 비드는 지르코니아 비드를 포함할 수 있다.In one aspect, the metal beads may include zirconia beads.
또한, 일 측면에서, 상기 1차 분산액을 얻는 단계는, 근적외선 차단능을 갖는 금속과, 중적외선 및 원적외선 차단능을 갖는 금속을 각각 분산시키는 것을 포함할 수 있다.Further, in one aspect, the obtaining of the first dispersion may include dispersing a metal having near-infrared ray blocking ability and a metal having mid-infrared ray and far-infrared ray blocking ability, respectively.
즉, 일 측면에서, 상기 방법은 i) 근적외선 차단능을 갖는 금속 및 ii) 중적외선 및 원적외선 차단능을 갖는 금속을 각각 분산 1차 분산 시킨 후, 각각을 다시 분산시켜 2차 분산액을 얻는 단계를 포함할 수 있다.That is, in one aspect, the method comprises i) a metal having a near-infrared ray blocking ability and ii) a metal having a mid-infrared ray and a far-infrared ray blocking ability, respectively, after primary dispersion, dispersing each again to obtain a secondary dispersion. can include
구체적으로, 상기 근적외선 차단능을 갖는 금속은, 메틸에틸케톤((Methyl ethyl ketone, MEK), 프로필렌 글리콜 모노에틸 에테르(Propylene glycol mono ethyl ether, PM), 및 프로필렌 글리콜 메틸 에테르(Propylene glycol methyl ether, PMA)로 구성된 군으로부터 선택된 유기용제 및 아민류의 혼합물에 분산시키는 것을 포함하고, 상기 중적외선 및 원적외선 차단능을 갖는 금속은, MEK, PM, 및 PMA로 구성된 군으로부터 선택된 유기용제 및 아크릴계 공중합체, 아민가 94 mg KOH/g, 산가 94 mg KOH/g, 및 밀도(20℃) 1.08 g/ml인 산기를 포함하는 알킬롤 암모늄 염(Alkylol ammonium salt of a copolymer with acidic groups), 및 아민류의 혼합물에 분산시키는 것을 포함할 수 있다.Specifically, the metal having the near-infrared ray blocking ability includes methyl ethyl ketone (MEK), propylene glycol monoethyl ether (PM), and propylene glycol methyl ether (Propylene glycol methyl ether, PMA) and an organic solvent selected from the group consisting of MEK, PM, and PMA, and an acrylic copolymer, Alkylol ammonium salt of a copolymer with acidic groups containing an acid group having an amine value of 94 mg KOH/g, an acid value of 94 mg KOH/g, and a density (20°C) of 1.08 g/ml, and a mixture of amines may include dispersing.
일 측면에서, 상기 근적외선은 파장이 0.78~2.5μm인 적외선을 의미할 수 있고, 상기 중적외선은 파장이 2.5~50μm인 적외선을 의미할 수 있고,상기 원적외선은 파장이 50~1000μm인 적외선을 의미할 수 있다.In one aspect, the near infrared ray may mean infrared rays having a wavelength of 0.78 to 2.5 μm, the mid-infrared rays may mean infrared rays having a wavelength of 2.5 to 50 μm, and the far infrared rays may mean infrared rays having a wavelength of 50 to 1000 μm. can do.
일 측면에서, 상기 분산 보조제는, 아크릴계 공중합체, 및 아민가 및 산가가 90 mg KOH/g 이상인 분산제를 더 포함할 수 있다.In one aspect, the dispersing aid may further include an acrylic copolymer, and a dispersing agent having an amine value and an acid value of 90 mg KOH/g or more.
상기 아민가 및 산가가 90 mg KOH/g 이상인 분산제는 예컨대, BYK사의 BYK-180일 수 있고, 아민가 94 mg KOH/g, 산가 94 mg KOH/g, 및 밀도(20℃) 1.08 g/ml인 산기를 포함하는 알킬롤 암모늄 염(Alkylol ammonium salt of a copolymer with acidic groups)일 수 있다.The dispersant having an amine value and an acid value of 90 mg KOH/g or more may be, for example, BYK-180 from BYK, an acid group having an amine value of 94 mg KOH/g, an acid value of 94 mg KOH/g, and a density (20° C.) of 1.08 g/ml It may be an alkylol ammonium salt of a copolymer with acidic groups.
상기 아크릴계 공중합체는 상표명 byk-2009(BYK社)와 같은 물질을 포함할 수 있으나, 이에 제한되는 것은 아니다.The acrylic copolymer may include a material such as the trade name byk-2009 (BYK Company), but is not limited thereto.
일 측면에서, 상기 방법은, 금속 분말을 분쇄하는 단계를 더 포함할 수 있다. 상기 분쇄는 밀링을 포함할 수 있으며, 일 구현예에서 상기 밀링은 지르코니아 비드와 같은 금속 비드를 이용하여 수행하는 것을 포함할 수 있다.In one aspect, the method may further include pulverizing the metal powder. The grinding may include milling, and in one embodiment, the milling may include performing using metal beads such as zirconia beads.
상기 분쇄하는 단계는 약 100시간 이상 수행될 수 있으나, 이에 제한되는 것은 아니다.The crushing step may be performed for about 100 hours or more, but is not limited thereto.
또한, 일 측면에서 상기 적외선 차단능을 갖는 금속의 평균 직경은 50nm 이하일 수 있다.In addition, in one aspect, the average diameter of the metal having the infrared ray blocking ability may be 50 nm or less.
또한, 상기 금속 분말을 분쇄한 후, 분쇄된 금속 분말의 평균 직경은 10μm 이하일 수 있다.In addition, after pulverizing the metal powder, the average diameter of the pulverized metal powder may be 10 μm or less.
또한, 일 측면에서, 상기 금속 분말과 수지를 혼합하여 마스터 배치를 제조하는 단계에서, 상기 금속 분말은 금속 분말과 수지의 혼합물의 총 중량을 기준으로, 5~20 중량%로 포함될 수 있다. In addition, in one aspect, in the step of preparing a master batch by mixing the metal powder and the resin, the metal powder may be included in an amount of 5 to 20% by weight based on the total weight of the mixture of the metal powder and the resin.
일 측면에서, 상기 적외선 차단능을 갖는 금속은, Cs2WO4 및 SnSb2O5 중 하나 이상을 포함할 수 있으나, 이에 제한되는 것은 아니며, W, Mo, In, Sb, Sn, Cs, Rb, V, Sr, Nb, 및 Cr 중 하나 이상을 포함할 수 있다.In one aspect, the metal having infrared blocking ability may include one or more of Cs 2 WO 4 and SnSb 2 O 5 , but is not limited thereto, and W, Mo, In, Sb, Sn, Cs, and Rb are not limited thereto. , V, Sr, Nb, and Cr.
일 측면에서, 상기 근적외선 차단능을 갖는 금속은 Cs2WO4일 수 있고, 상기 중적외선 및 원적외선 차단능을 갖는 금속은 SnSb2O5 일 수 있다.In one aspect, the metal having the ability to block near-infrared rays may be Cs 2 WO 4 , and the metal having the ability to block mid-infrared rays and far-infrared rays may be SnSb 2 O 5 .
또한, 일 측면에서, 상기 아민류는 n,n-디메틸에탄올아민을 포함할 수 있으나, 이에 제한되는 것은 아니며, 상기 포화지방산은 스테아린산을 포함할 수 있으나, 이에 제한되는 것은 아니다. Also, in one aspect, the amines may include n,n-dimethylethanolamine, but are not limited thereto, and the saturated fatty acid may include stearic acid, but is not limited thereto.
이하, 제조예, 실시예 및 실험예를 들어 본 발명의 구성 및 효과를 보다 구체적으로 설명한다. 그러나 이들 실시예 및 시험예는 본 발명에 대한 이해를 돕기 위해 예시의 목적으로만 제공된 것일 뿐 본 발명의 범주 및 범위가 하기 예에 의해 제한되는 것은 아니다.Hereinafter, the configuration and effects of the present invention will be described in more detail by way of manufacturing examples, examples and experimental examples. However, these examples and test examples are provided only for illustrative purposes to aid understanding of the present invention, and the scope and scope of the present invention are not limited by the following examples.
[제조예][Production Example]
메틸에틸케톤, 프로필렌 글리콜 모노에틸 에테르 및 프로필렌 글리콜 메틸 에테르 중 하나의 용제, 적외선 차단 금속, 보조 분산제인 byk-180 및 n,n-Dimethylethanolamine을 각각 약 78: 18: 4.5: 0.5의 함량비로 혼합하여 금속 분말을 분산시킨 1차 분산액을 제조하였다.A solvent of one of methyl ethyl ketone, propylene glycol monoethyl ether and propylene glycol methyl ether, an infrared ray blocking metal, byk-180 as an auxiliary dispersant, and n,n-Dimethylethanolamine are mixed at a content ratio of about 78: 18: 4.5: 0.5, respectively. A primary dispersion liquid in which the metal powder was dispersed was prepared.
이 때, 적외선 차단 금속은 Cs2WO4 및 SnSb2O5를 동량 사용하였으며, 각각을 분산시켰다. 상기 분산 후 습윤 공정으로 습기를 제거한 후, 지르코니아 재질의 비드와 볼 밀링 머신을 이용하여 100시간 이상 천천히 milling 하였다.At this time, the same amount of Cs 2 WO 4 and SnSb 2 O 5 was used as the infrared blocking metal, and each was dispersed. After the dispersion was followed by removing moisture through a wetting process, the mixture was slowly milled for 100 hours or more using a zirconia bead and a ball milling machine.
그 후 상기 2종의 1차 분산액을 과량의 스테아린산(1차 분산액 내 고형분 중량 대비 약20~50%) 에 혼합한 후, 지르코니아 재질의 볼밀을 이용하여 충분히 milling을 수행하였다.Thereafter, the two primary dispersions were mixed with an excess of stearic acid (about 20 to 50% by weight of solid content in the primary dispersion), and then milling was sufficiently performed using a zirconia ball mill.
그 후, Spray 또는 tray 건조를 통해 용제 잔량이 1% 미만이 되도록 건조하여, 마스터배치용 분말을 제조한 후, 비닐하우스용 폴리에틸렌 수지에 상기 분말을 약 15중량% 첨가하여 혼합하여, 마스터 배치를 제조하였다. After that, drying the remaining solvent to less than 1% through spray or tray drying to prepare a master batch powder, and then adding about 15% by weight of the powder to a polyethylene resin for a vinyl house and mixing to obtain a master batch. manufactured.
그 후 제조한 마스터 배치를 압출하여 비닐하우스용 필름을 제조하였다. Thereafter, a film for a vinyl house was prepared by extruding the prepared master batch.
[실험예] [Experimental example]
[실험예 1] 필름의 가시광선 투과율 및 열차단 효과 확인[Experimental Example 1] Confirmation of visible light transmittance and thermal blocking effect of film
상기 제조예 1에서 제조한 필름에 대하여 가시광선 투과율, 투명도, 열차단 효과를 확인하였다. 비교군으로는 시중의 일반적인 PO 필름과 PE 필름을 사용하였다. The visible light transmittance, transparency, and heat shielding effect of the film prepared in Preparation Example 1 were confirmed. Commercially available PO films and PE films were used as comparative groups.
가시광선 투과율과 열차단 효과는, 일본 JASCO사의 V-670 SPECTROPHPTPMETER를 통해 측정하였다.Visible light transmittance and thermal blocking effect were measured using V-670 SPECTROPHPTPMETER manufactured by JASCO, Japan.
그 결과, 제조예의 필름과 시중의 필름은 유사한 수준의 가시광선 투과율과 투명도를 나타내었으나, 적외선 차단율에 있어, 950nm 파장의 적외선에 대하여 제조예 필름의 차단율이 약 28.5%인데 반하여, PO 필름은 약 16.2%, PE 필름이 약 13.1%의 차단율을 나타내었고, 1400nm 파장의 적외선에 대하여 제조예 필름의 차단율은 33%인데 반하여, PO 필름과 PE 필름은 각각 약 12.2% 및 10.1%의 차단율을 나타내어, 본원발명의 필름의 적외선 차단율이 월등히 우수함을 확인할 수 있었다.As a result, the film of Preparation Example and the film on the market showed similar levels of visible light transmittance and transparency, but in terms of infrared blocking rate, the film of Preparation Example had a blocking rate of about 28.5% for infrared rays with a wavelength of 950 nm, whereas the PO film had about 28.5%. 16.2%, the PE film showed a blocking rate of about 13.1%, and the blocking rate of the prepared film was 33% for infrared rays of 1400 nm wavelength, whereas the PO film and the PE film showed a blocking rate of about 12.2% and 10.1%, respectively, It was confirmed that the infrared ray blocking rate of the film of the present invention was far superior.
또한, 본 발명의 필름의 열차단율은 상기 시중의 필름과 비교하여 2배 이상 우수한 것을 알 수 있었다.In addition, it was found that the thermal barrier rate of the film of the present invention was more than twice as good as that of the commercially available film.
[실험예 2] 적외선 측정[Experimental Example 2] Infrared measurement
제조예 필름을 제작하여 적외선 차단율을 상온에서 측정하였다. 본 제품은 500ppm 의 열차단 재료를 함유한 재료이며, 그 결과 상온에서 투과도 변화가 거의 없이 약 29.3%의 차단율을 나타내었다. Preparation Example A film was prepared and the infrared ray blocking rate was measured at room temperature. This product is a material containing 500ppm of thermal barrier material, and as a result, it showed a blocking rate of about 29.3% with little change in transmittance at room temperature.
Claims (10)
상기 1차 분산액을 포화지방산에 분산시켜, 2차 분산액을 얻는 단계;
상기 2차 분산액을 건조하여 금속 분말을 얻는 단계; 및
상기 금속 분말과 수지를 혼합하는 단계를 포함하는, 온실 필름용 마스터배치의 제조방법.Contains organic solvents and amines selected from the group consisting of methyl ethyl ketone (MEK), propylene glycol mono ethyl ether (PM), and propylene glycol methyl ether (PMA) dispersing a metal having infrared ray blocking ability in a mixture of dispersing aids to obtain a primary dispersion;
dispersing the first dispersion in saturated fatty acid to obtain a second dispersion;
drying the secondary dispersion to obtain metal powder; and
A method for producing a master batch for a greenhouse film, comprising mixing the metal powder and the resin.
상기 1차 분산액을 얻는 단계는,
근적외선 차단능을 갖는 금속과, 중적외선 및 원적외선 차단능을 갖는 금속을 각각 분산시키는 것을 포함하는, 온실 필름용 마스터배치의 제조방법.According to claim 1,
Obtaining the first dispersion,
A method for producing a masterbatch for a greenhouse film comprising dispersing a metal having near-infrared ray blocking ability and a metal having mid-infrared ray and far-infrared ray blocking ability, respectively.
상기 분산 보조제는,
아크릴계 공중합체; 및 아민가 및 산가가 90mg KOH/g 이상인, 알킬롤 암모늄 염(alkylol ammonium salt)을 더 포함하는, 온실 필름용 마스터배치의 제조방법.According to claim 1,
The dispersing aid,
acrylic copolymers; and an alkylol ammonium salt having an amine value and an acid value of 90 mg KOH/g or more.
상기 방법은, 금속 분말을 분쇄하는 단계를 더 포함하는 온실 필름용 마스터배치의 제조방법.According to claim 1,
The method of manufacturing a master batch for a greenhouse film further comprising the step of pulverizing the metal powder.
상기 적외선 차단능을 갖는 금속의 평균 직경은 50nm 이하인, 온실 필름용 마스터배치의 제조방법.According to claim 1,
The average diameter of the metal having the infrared ray blocking ability is 50 nm or less, a method for producing a master batch for a greenhouse film.
상기 금속 분말을 분쇄한 후, 분쇄된 금속 분말의 평균 직경은 10μm 이하인, 온실 필름용 마스터배치의 제조방법. According to claim 4,
After pulverizing the metal powder, the average diameter of the pulverized metal powder is 10 μm or less, a method for producing a master batch for a greenhouse film.
금속 분말과 수지를 혼합하는 단계에서,
상기 금속 분말은 금속 분말과 수지의 혼합물의 총 중량을 기준으로, 5~20 중량%로 포함되는, 온실 필름용 마스터배치의 제조방법.According to claim 1,
In the step of mixing the metal powder and the resin,
The metal powder is included in 5 to 20% by weight based on the total weight of the mixture of the metal powder and the resin, a method for producing a master batch for a greenhouse film.
상기 근적외선 차단능을 갖는 금속은, MEK, PM, 및 PMA로 구성된 군으로부터 선택된 유기용제 및 아민류의 혼합물에 분산시키는 것을 포함하고,
상기 중적외선 및 원적외선 차단능을 갖는 금속은, MEK, PM, 및 PMA로 구성된 군으로부터 선택된 유기용제 및 아크릴계 공중합체, 아민가 및 산가가 90mg KOH/g 이상인, 알킬롤 암모늄 염(alkylol ammonium salt), 및 아민류의 혼합물에 분산시키는 것을 포함하는, 온실 필름용 마스터배치의 제조방법.According to claim 2,
The metal having near-infrared ray blocking ability includes dispersing in a mixture of an organic solvent and amines selected from the group consisting of MEK, PM, and PMA,
The metal having mid-infrared and far-infrared ray blocking ability is an organic solvent and an acrylic copolymer selected from the group consisting of MEK, PM, and PMA, an amine value and an acid value of 90 mg KOH / g or more, an alkylol ammonium salt, And a method for producing a masterbatch for a greenhouse film comprising dispersing in a mixture of amines.
상기 적외선 차단능을 갖는 금속은, Cs2WO4 및 SnSb2O5 중 하나 이상을 포함하는, 온실 필름용 마스터배치의 제조방법. According to claim 1,
The method of manufacturing a masterbatch for a greenhouse film, wherein the metal having infrared blocking ability includes at least one of Cs 2 WO 4 and SnSb 2 O 5 .
상기 아민류는, n,n-디메틸에탄올아민을 포함하고,
상기 포화지방산은, 스테아린산을 포함하는, 온실 필름용 마스터배치의 제조방법.According to claim 1,
The amines include n,n-dimethylethanolamine,
The method for producing a master batch for a greenhouse film, wherein the saturated fatty acid comprises stearic acid.
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