KR100682715B1 - Water-resisting agent for starch manufactured fried bowl - Google Patents
Water-resisting agent for starch manufactured fried bowl Download PDFInfo
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- KR100682715B1 KR100682715B1 KR1020060001648A KR20060001648A KR100682715B1 KR 100682715 B1 KR100682715 B1 KR 100682715B1 KR 1020060001648 A KR1020060001648 A KR 1020060001648A KR 20060001648 A KR20060001648 A KR 20060001648A KR 100682715 B1 KR100682715 B1 KR 100682715B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
Abstract
Description
본 발명은 전분을 이용하여 제조된 유탕용기의 내수처리제에 관한 것으로, 더욱 상세하게는 유탕용기에 내수성은 물론 부착성, 불점착성, 내황변성 등을 제공하기 위하여 전분과 혼합한 후 성형하는 내부첨가 방법에서 뿐만 아니라 담금이나 분무 등에 의한 처리에서도 양호한 특성을 나타내는 내수처리제에 관한 것이다.The present invention relates to a water treatment agent for a milk container prepared using starch, and more particularly, to an oil-containing container added after mixing with starch to provide water resistance as well as adhesion, non-adhesiveness, and yellowing resistance. It relates to a water treatment agent exhibiting good properties not only in the method but also in the treatment by immersion, spraying or the like.
현재 사용되는 1회용 식품 포장 용기는 종이 또는 펄프몰드나 플라스틱 물질의 성형품 등이 주종으로서, 종이 또는 펄프몰드를 이용한 용기는 폐기 처리 측면에서는 친환경적이기는 하나 원료자체가 다년생 식물을 원료로 한다는 점에서 원료 조달 측면으로는 그다지 친환경적이지 못하다.Currently used disposable food packaging containers are mainly made of paper or pulp molds or plastic materials. Containers made of paper or pulp molds are eco-friendly in terms of disposal, but the raw materials themselves are perennial plants. In terms of procurement, it is not very environmentally friendly.
또한 폴리스티렌, 폴리에틸렌, 폴리프로필렌, 폴리비닐클로라이드 등의 플라스틱 물질의 성형품으로 이루어진 물질은 인체에 유해한 환경저해물질로 인해 사용상 많은 문제를 일으키며, 완전한 재활용이 불가능하고, 일반적인 폐기처리 방법이 소각 또는 매립 방법 밖에 없어 환경 오염의 문제점이 있다.In addition, materials made of molded articles of plastic materials such as polystyrene, polyethylene, polypropylene, and polyvinyl chloride may cause many problems in use due to environmentally harmful substances that are harmful to the human body, and cannot be completely recycled. There is only a problem of environmental pollution.
이에 대하여 전분을 이용하여 제조되는 1회용 유탕용기는 감자나 옥수수, 타 피오카 등의 1년생 식물의 녹말을 원료원으로 하기 때문에 제조 및 폐기시에 인체에 무해하고 환경오염이 전혀 없는 가장 친환경적인 소재라 할 수 있다.On the other hand, the disposable milk container produced using starch is made from starch of annual plants such as potatoes, corn, and tapioca as raw materials, so it is harmless to human body and no environmental pollution during manufacturing and disposal. It can be called material.
그러나, 전분몰드는 식품을 담았을 때 점착성, 물의 침투 등의 문제점 때문에 널리 사용하기에는 많은 문제점이 있어서 유탕 용기로 상업화된 제품이 아직까지 없었으며, 일부에서 전분 용기표면에 왁스 등을 분산시켜 내수성을 강화하려는 시도가 있었으나, 내수성은 일부 나타내지만 열수에 취약한 단점 때문에 널리 사용되지 못하는 실정이었다.However, starch mold has many problems to be widely used due to problems such as stickiness and water penetration when food is contained, and there have been no commercialized products for lactose containers. Attempts have been made to improve the water resistance, but some of the water resistance is not widely used due to the weakness of the hot water.
본 발명에서 이루고자 하는 첫 번째 기술적 과제는 전분을 이용하여 제조된 1회용 유탕 용기에 수분산성이면서, 부착성, 불첨착성 및 내황변성 등을 동시에 나타내는 내수처리제를 제공하는 것으로 이것은 일반적인 표면처리 방법은 물론 내부첨가 방법을 통해서도 내수성을 나타낸다. 본 발명이 이루고자 하는 두 번째 기술적 과제는 본 제품의 제조 과정은 물론 유탕 용기에 처리할 때에도 유기 용제를 사용하지 않음으로서 인체에 대한 유해도가 적으면서, 화재의 위험과 용제 증발에 의한 대기 환경오염 없는 전분 몰드로 제조된 1회용 유탕 용기의 내수처리제를 제공하는 것이다.The first technical problem to be achieved in the present invention is to provide a water-resistant treatment agent that exhibits water dispersibility and adhesion, non-adhesiveness, and yellowing resistance at the same time in a disposable milk container prepared using starch. It also shows water resistance through internal addition method. The second technical problem to be achieved by the present invention is that the organic solvent is not used in the manufacturing process of the product as well as in the processing of the lacquer container, so that there is little danger to the human body, and there is a risk of fire and air pollution due to solvent evaporation. It is to provide a water-resistant agent for a disposable milk container made of starch mold free.
상기 첫 번째 기술적 과제를 달성하기 위하여 본 발명은 글리세린 모노알릴 에테르 반복단위(A), 수산기를 함유하는 락톤변성 불포화 알릴 에테르 반복단위(B), 아크릴산 에스테르 반복단위(C), 메타크릴산에스테르 반복단위(D)를 포함하는 것을 특징으로 하는 하기 화학식 1의 수분산성 유화중합체를 제공한다.In order to achieve the first technical problem, the present invention is glycerin monoallyl ether repeating unit (A), lactone-modified unsaturated allyl ether repeating unit (B) containing a hydroxyl group, acrylic ester repeating unit (C), methacrylic acid ester repeating It provides a water dispersible emulsion of the formula (1) comprising the unit (D).
[화학식 1][Formula 1]
(상기 식 1에서, R1 은 수소 또는 탄소수 1 내지 8인 알킬기에서 선택된 어느 하나이고, R2 는 수소 또는 탄소수 1 내지 8인 알킬기에서 선택된 어느 하나이며, k, l, m, n은 양의 수이고 q는 2또는 5이다.)(In Formula 1, R 1 is any one selected from hydrogen or an alkyl group having 1 to 8 carbon atoms, R 2 is any one selected from hydrogen or an alkyl group having 1 to 8 carbon atoms, k, l, m, n is a positive Number and q is 2 or 5.)
본 발명의 일 실시예에 의하면, 상기 고분자중 각 반복단위의 함량은 글리세린 모노 알릴 에테르 반복단위(A) 1내지 20 중량부, 수산기를 함유하는 락톤변성 불포화 알릴 에테르 반복단위(B) 1내지 20 중량부, 아크릴산 에스테르 반복단위(C) 5내지 90 중량부, 메타크릴산에스테르 반복단위(D) 5내지 90 중량부인 것이 바람직하며, 본 발명의 수분산성 유화중합체의 중량평균분자량은 150,000 내지 350,000인 것이 바람직하다.According to one embodiment of the present invention, the content of each repeating unit in the polymer is 1 to 20 parts by weight of glycerin monoallyl ether repeating unit (A), lactone-modified unsaturated allyl ether repeating unit (B) 1 to 20 containing hydroxyl groups By weight, acrylic acid ester repeating unit (C) 5 to 90 parts by weight, methacrylic acid ester repeating unit (D) is preferably 5 to 90 parts by weight, the weight average molecular weight of the water-dispersible emulsion polymer of the present invention is 150,000 to 350,000 It is preferable.
또한 상기 두 번째 기술적 과제를 달성하기 위하여 본 발명에 따른 전분을 이용한 1회용 유탕용기의 내수처리제는 상기 수분산성 유화중합체를 포함하는 것을 특징으로 한다.In addition, in order to achieve the second technical problem, the water treatment agent of the disposable lactose container using starch according to the present invention is characterized in that it comprises the water-dispersible emulsion polymer.
이하에서는 본 발명에 따른 수분산성 유화중합체에 대하여 상세히 설명하기로 한다. 본 발명에 따른 내수처리제로 사용되는 수분산성 유화중합제는 주사슬에 글리세린 모노알릴 에테르 반복단위(A), 수산기를 함유하는 락톤변성 불포화 알릴 에테르 올리고머 반복단위(B), 아크릴산 에스테르 반복단위(C), 메타크릴산에스테르 반복단위(D)를 포함한다.Hereinafter will be described in detail with respect to the water-dispersible emulsion polymer according to the present invention. The water-dispersible emulsion polymerization agent used as the water treatment agent according to the present invention is a glycerin monoallyl ether repeating unit (A) in the main chain, a lactone-modified unsaturated allyl ether oligomer repeating unit (B) containing a hydroxyl group, an acrylic ester repeating unit (C ) And methacrylic acid ester repeating units (D).
일반적으로 알려진 아크릴 에멀젼 고분자는 우수한 물성을 나타내나, 내수성 및 불점착성 등은 좋지 않을 수 있다. 이러한 점을 개선하기 위하여 본 발명에서는 기존의 아크릴 중합체에 글리세린 모노알릴 에테르 반복단위 및 수산기를 함유하는 락톤변성 불포화 알릴 에테르 반복단위를 더 도입함으로서 내수성 및 불점착성 등의 물성을 크게 향상 시키는 것을 특징으로 한다. 이와 같은 글리세린 모노알릴 에테르 반복단위 및 수산기를 함유하는 락톤변성 불포화 알릴 에테르 반복단위를 도입함으로서 중합체와 전분간의 친화력이 커져서 피막의 밀착성과 탄성이 향상되어 표면의 갈라짐 현상이 방지되고, 저온 유연성, 내후성, 내수성 등이 더욱 향상되는 특징을 나타낸다. 그리고, 본 발명에 따른 수분산성 유화중합체는 부착성과 수분산성이 좋게 되어 종래의 아크릴레이트와는 달리 유기용제를 사용하지 않아도 되므로 유기용제를 사용함으로서 발생할 수 있는 화재 및 폭발을 방지할 수 있고, 특히 유기용제의 증발에 의한 대기 오염을 낮출 수 있다.Generally known acrylic emulsion polymers exhibit excellent physical properties, but water resistance and non-tackiness may not be good. In order to improve this point, in the present invention, by further introducing a lactone-modified unsaturated allyl ether repeating unit containing a glycerin monoallyl ether repeating unit and a hydroxyl group to the existing acrylic polymer, it is characterized in that the physical properties such as water resistance and non-tackiness are greatly improved. do. By introducing such a glycerin monoallyl ether repeating unit and a lactone-modified unsaturated allyl ether repeating unit containing a hydroxyl group, the affinity between the polymer and the starch is increased, thereby improving the adhesion and elasticity of the film to prevent surface cracking, low temperature flexibility and weather resistance , Water resistance and the like are further improved. In addition, the water-dispersible emulsion polymer according to the present invention has good adhesion and water dispersibility, so unlike the conventional acrylates do not need to use an organic solvent, it is possible to prevent the fire and explosion that can occur by using an organic solvent, in particular The air pollution by the evaporation of the organic solvent can be reduced.
본 발명에 의한 중합체는 글리세린 모노알릴 에테르 반복단위(A) 및 수산기를 함유하는 락톤변성 불포화 알릴 에테르 반복단위(C), 아크릴산 에스테르 반복단 위(C), 메타크릴산에스테르 반복단위(D)의 함량은 내수처리제가 사용되는 방법 및 내수성, 불점착성, 부착성, 균일성 등과 같이 요구되는 물성에 따라 변화시킬 수 있으며, 일반적으로는 각각 1 내지 20 중량부, 1 내지 20 중량부, 5 내지 90 중량부 및 5 내지 90 중량부로 이루어진 것을 사용하는 것이 바람직하다.The polymer according to the present invention is composed of a glycerin monoallyl ether repeating unit (A) and a lactone-modified unsaturated allyl ether repeating unit (C) containing a hydroxyl group, an acrylic acid ester repeating unit (C), and a methacrylic acid ester repeating unit (D). The content can be changed depending on the method in which the water treatment agent is used and the required physical properties such as water resistance, non-tackiness, adhesion, uniformity, etc., generally 1 to 20 parts by weight, 1 to 20 parts by weight, and 5 to 90 parts, respectively. Preference is given to using those consisting of parts by weight and 5 to 90 parts by weight.
또한, 수분산성유화중합체의 유연성, 탄성, 부착력, 내수성, 불점착성, 내황변성 등을 고려할 때 중량 평균분자량은 150,000내지 350,000인 것이 바람직하다.In addition, the weight average molecular weight is preferably 150,000 to 350,000 in consideration of the flexibility, elasticity, adhesion, water resistance, non-adhesiveness, yellowing resistance and the like of the water-dispersible emulsion polymer.
본 발명에 따른 중합체는 각각의 반복단위가 선상으로 이루어져 있으며, 불규칙하게 배열된 랜덤 코폴리머 형태 또는 각각 반복단위로 이루어진 블록 코폴리머의 형태 등 어떤 형태로 이루어져 있어도 무방하며, 특히 본 발명에 따른 반복단위를 저하시키지 않는 범위 내에서 다른 반복단위를 더 공중합시킬 수 있다.The polymer according to the present invention may be in any form, such as in the form of random copolymers arranged randomly or in the form of block copolymers each consisting of repeating units, and in particular, the repeating unit according to the present invention. Other repeating units may be further copolymerized within the range of not lowering the unit.
본 발명의 수분산성 내수처리제 제조시 물성을 향상시키기 위하여 소포제, 동결방지제 또는 분산제 및 안정제로서 각종 계면활성제 중 하나 이상의 첨가제를 0.01내지 5중량 %를 사용한다.0.01 to 5% by weight of one or more additives of various surfactants is used as an antifoaming agent, an antifreezing agent or a dispersant, and a stabilizer in order to improve physical properties in the preparation of the water dispersible water treatment agent of the present invention.
이하 본 발명을 실시예를 통해 더욱 상세히 설명하나, 본 발명이 하기 실시예로 인해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
실시예 1Example 1
1,000mL 4구 플라스크에 온도계, 질소주입구, 냉각기 및 모터에 의한 강력교반기를 설치하였다. 여기에 과황산암모늄 1.3중량부, 노닐페놀에톡시레이트 10부가물 2.5중량부, 아크릴산 단량체 3 중량부, 부틸아크릴레이트 단량체 50중량부를 함유한 180중량부의 물을 반응 용매로 하여 질소 기류 중에서 교반시키면서 반응기내 의 온도를 78℃까지 서서히 올린다. 그리고 1,000mL 비이커에서 물 150중량부, 유화제로서 노닐페놀에톡시레이트 10부가물 5.5중량부와 부틸아크릴레이트 단량체 95 중량부, 메틸메타크릴레이트 단량체 82 중량부, 아크릴산 단량체 7중량부, 2-하이드록시에틸메타크릴레이트 8 중량부, 글리세린 알릴 에테르 단량체 13 중량부, 수산기함유 락톤(2부가물)변성 불포화 알릴 에테르 단량체 10중량부를 가하여 유화시킨다. 다음에 이 혼합물을 적하깔때기를 통하여 급격한 발열이 일어나지 않도록 반응기로 서서히 적하시킨다. 반응 온도를 78℃로 잘 유지시키면서 약 7시간의 중합반응을 통하여 고형분 45내지 48 중량 %이고, 중량 평균 분자량 250,000인 수분산성 유화중합체를 얻었다.A 1,000 mL four-necked flask was equipped with a strong stirrer by thermometer, nitrogen inlet, cooler and motor. 180 parts by weight of water containing 1.3 parts by weight of ammonium persulfate, 2.5 parts by weight of 10 parts of nonylphenol ethoxylate, 3 parts by weight of acrylic acid monomer and 50 parts by weight of butyl acrylate monomer as a reaction solvent, while stirring in a nitrogen stream. Slowly increase the temperature in the reactor to 78 ℃. And 150 parts by weight of water in a 1,000 mL beaker, 5.5 parts by weight of nonylphenol ethoxylate 10 parts by weight of emulsifier, 95 parts by weight of butyl acrylate monomer, 82 parts by weight of methyl methacrylate monomer, 7 parts by weight of acrylic acid monomer, 2-hydro Eight parts by weight of oxyethyl methacrylate, 13 parts by weight of glycerin allyl ether monomer, and 10 parts by weight of hydroxyl group-containing lactone (divalent) modified unsaturated allyl ether monomer are added and emulsified. This mixture is then slowly added dropwise into the reactor to avoid rapid exotherm through the dropping funnel. A water dispersible emulsion having a solid content of 45 to 48% by weight and a weight average molecular weight of 250,000 was obtained through polymerization of about 7 hours while maintaining the reaction temperature at 78 ° C.
실시예 2Example 2
글리세린 알릴 에테르 단량체를 20 중량부, 수산기함유 락톤(2부가물)변성 불포화 알릴 에테르 단량체를 5중량부 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 수분산성 유화중합체를 얻었다.A water dispersible emulsion polymer was obtained in the same manner as in Example 1, except that 20 parts by weight of glycerin allyl ether monomer and 5 parts by weight of hydroxyl group-containing lactone (divalent) modified unsaturated allyl ether monomer were added.
실시예 3Example 3
수산기함유 락톤(5부가물)변성 불포화 알릴 에테르 단량체를 10중량부 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 수분산성 유화중합체를 얻었다.A water dispersible emulsion polymer was obtained in the same manner as in Example 1 except that 10 parts by weight of a hydroxyl group-containing lactone (5-addition) modified unsaturated allyl ether monomer was added.
실험예 1Experimental Example 1
상기 실시예에 따라 제조된 내수처리제를 전분 용기를 만들기 위한 전분과 펄프 혼합물에 5중량 %로 함께 혼합한 후 몰드 성형하여 45℃에서 15시간 숙성시킨 후 전분 용기 표면에 형성된 도막의 물성을 측정한 결과를 표 1에 나타내었다.After mixing the water-resistant treatment agent prepared according to the above example in a starch and pulp mixture to make a starch container at 5% by weight together, and then molded and aged at 45 ℃ for 15 hours to measure the physical properties of the coating film formed on the surface of the starch container The results are shown in Table 1.
실험예 2Experimental Example 2
상기 실시예에 따라 제조된 내수처리제를 중량비로서 물과 4:1의 비율로 혼합한 후 이미 성형된 전분 용기에 건조 도막이 25㎛이 되도록 표면 처리를 한 다음 150℃로 유지되는 열풍 건조기에서 3분간 건조시키고, 전분 용기 표면에 형성된 도막의 물성을 측정한 결과를 표 2에 나타내었다.After mixing the water-resistant treatment agent prepared according to the above embodiment in a weight ratio of water with a ratio of 4: 1, the surface of the already formed starch container was surface treated to have a dry coating thickness of 25 μm and then maintained at 150 ° C. for 3 minutes. The result of having measured the physical property of the coating film formed on the surface of the dried starch container is shown in Table 2.
실시예 1내지 3에 의하여 제조된 표면처리제를 실험예 1내지 2에 의한 평가 결과는 일반적으로 널리 사용되는 방법을 이용하였다. 즉, 내수성은 90℃ 물에 삼투되지 않는 정도를 측정하였으며, 부착성은 스카치테이프를 붙이고, 1cm×1cm의 면적을 100등분한 후 탈리되는 정도를 비교하였다. 불점착성은 의료용 거즈를 내수처리제가 처리된 용기의 표면에 놓고 60℃로 유지되는 항온조 속에 넣고 거즈 자국이 남는 시간을 측정하였다. 또한, 균일(levelling)성은 20번 바(bar)를 이용하여 코팅하였을 때, 평활하게 되는 정도를 측정하였으며, 내황변성은 210℃로 유지되는 항온조 속에 측정 용기를 넣고 표면에 황변이 나타나는 시간을 측정하였다.As a result of evaluating the surface treatment agent prepared in Examples 1 to 3 by Experimental Examples 1 to 2, a method widely used was generally used. That is, the water resistance was measured the degree of not osmosis in water at 90 ℃, the adhesion was attached to the scotch tape, and compared to the degree of detachment after dividing the area of 1cm × 1cm 100 times. Non-adhesiveness was measured by placing the medical gauze on the surface of the container treated with a water treatment agent and placing it in a thermostat maintained at 60 ° C. In addition, the leveling property was measured to the degree of smoothing when the coating using a 20 bar (bar), yellowing resistance is measured in a thermostat maintained at 210 ℃ in the temperature measuring the time the yellowing appears on the surface It was.
[표 1]TABLE 1
[표 2]TABLE 2
상기 표 1과 표2의 결과를 토대로 본 발명에 따른 내수처리제로 형성된 전분 용기의 표면 도막은 내수성, 불점착성, 부착성 및 균일성, 내황변성 등이 우수하여 1회용 전분 용기의 내부첨가형 또는 표면처리용 내수처리제로 사용하는 데 아무런 문제가 없음을 알 수 있다.Based on the results of Table 1 and Table 2, the surface coating film of the starch container formed with the water treatment agent according to the present invention is excellent in water resistance, non-tackiness, adhesion and uniformity, yellowing resistance, etc. It can be seen that there is no problem in using it as a water treatment agent for treatment.
본 발명의 글리세린 모노알릴 에테르 반복단위와 수산기를 함유하는 락톤변성불포화 알릴에테르 올리고머 및 여러 가지 아크릴레이트를 포함하는 수분산성 유화중합체인 내수처리제는 내수성, 불점착성, 부착성, 균일성 및 내황변성 등이 우수하여 용기에 수분이 포함된 식품을 담아도 붙거나 팽윤되는 것을 방지할 수 있고, 특히 침수로 인한 용기의 기능 저하를 방지하는 데 아무런 문제가 없다. 또한, 유기 용제의 사용이 없어서 내수처리제의 제조 및 용기의 생산 공정에서도 인체에 유해하지 않을 뿐만 아니라 제품 사용 도중 및 사용 후에도 환경오염의 문제가 없고 전분 용기의 매립에 의한 폐기 처리시 자연 분해 효과가 저해되지 않아 전분을 이용하여 제조된 1회용 유탕 용기의 친환경적 내수처리제로서 유용하게 사용될 수 있다.The water treatment agent, which is a water-dispersible emulsion polymer containing a glycerol monoallyl ether repeating unit and a hydroxyl group containing a lactone-modified unsaturated allyl ether oligomer and various acrylates, includes water resistance, non-tackiness, adhesion, uniformity, yellowing resistance, and the like. It is excellent in that it is possible to prevent the container from sticking or swelling even if it contains food containing water, in particular, there is no problem in preventing the deterioration of the container due to immersion. In addition, since there is no use of organic solvents, it is not harmful to the human body in the manufacturing process of the water treatment agent and the container, and there is no problem of environmental pollution during and after the use of the product. Since it is not inhibited, it may be usefully used as an environmentally friendly water treatment agent of a disposable lactation container manufactured using starch.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4282203A (en) | 1978-10-27 | 1981-08-04 | L'oreal | Hair lacquer and hair lotion compositions containing a copolymer having units of a vinyl allyl or methally ester of an α- or β-cyclic carboxylic acid |
| KR930001805B1 (en) * | 1989-10-02 | 1993-03-13 | 브리스톨-마이어즈 스퀴브 컴페니 | Tretinoin emulsified cream formulations of improved stability |
| EP1101857A2 (en) | 1999-11-16 | 2001-05-23 | National Starch and Chemical Investment Holding Corporation | Textile manufacturing and treating processes using a hydrophobically modified polymer |
| KR20030093514A (en) * | 2002-06-03 | 2003-12-11 | 주식회사 엘지화학 | Photosensitive composition for liquid crystal display and black matrix comprising thereof |
-
2006
- 2006-01-06 KR KR1020060001648A patent/KR100682715B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4282203A (en) | 1978-10-27 | 1981-08-04 | L'oreal | Hair lacquer and hair lotion compositions containing a copolymer having units of a vinyl allyl or methally ester of an α- or β-cyclic carboxylic acid |
| KR930001805B1 (en) * | 1989-10-02 | 1993-03-13 | 브리스톨-마이어즈 스퀴브 컴페니 | Tretinoin emulsified cream formulations of improved stability |
| EP1101857A2 (en) | 1999-11-16 | 2001-05-23 | National Starch and Chemical Investment Holding Corporation | Textile manufacturing and treating processes using a hydrophobically modified polymer |
| KR20030093514A (en) * | 2002-06-03 | 2003-12-11 | 주식회사 엘지화학 | Photosensitive composition for liquid crystal display and black matrix comprising thereof |
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