KR101181253B1 - Polyurethane Additive Composition for Suppressing the Scorching Phenomenon Occurred When Polyurethane Foam is Discharged and Method for Preparing the Same - Google Patents
Polyurethane Additive Composition for Suppressing the Scorching Phenomenon Occurred When Polyurethane Foam is Discharged and Method for Preparing the Same Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/00—Use of organic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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- C08K5/52—Phosphorus bound to oxygen only
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Abstract
본 발명은 용매 5 내지 30 중량%, 힌더드 페놀계 산화방지제 5 내지 20 중량%, 방향족 아민계 산화방지제 10 내지 40 중량%, 및 포스파이트계 산화방지제 30 내지 80 중량%로 이루어지는 폴리우레탄 첨가제 조성물을 제공한다. 또한 본 발명은 수분이 제거된 반응조에 용매 5 내지 30 중량% 및 액상의 포스파이트계 산화방지제 30 내지 80 중량%를 투입하여 온도를 50 내지 100 ℃ 까지 올리면서 교반하고, 그리고 상기 반응조에 힌더드 페놀계 산화방지제 5 내지 20 중량% 및 방향족 아민계 산화방지제 10 내지 40 중량%를 투입하여 용해시킨 후 온도를 50 내지 100 ℃ 유지시키면서 60 내지 200 분 동안 중합하는 단계로 제조되는 것을 특징으로 하는 폴리우레탄 첨가제 조성물의 제조방법을 제공한다.The present invention is a polyurethane additive composition comprising 5 to 30% by weight of solvent, 5 to 20% by weight of hindered phenolic antioxidant, 10 to 40% by weight of aromatic amine antioxidant, and 30 to 80% by weight of phosphite antioxidant. To provide. In another aspect, the present invention by adding 5 to 30% by weight of the solvent and 30 to 80% by weight of the liquid phosphite-based antioxidant in the reaction tank is removed while stirring while raising the temperature to 50 to 100 ℃, and hindered in the reactor 5 to 20% by weight of a phenolic antioxidant and 10 to 40% by weight of an aromatic amine antioxidant are dissolved, followed by polymerization for 60 to 200 minutes while maintaining a temperature of 50 to 100 ℃ poly Provided is a method of preparing a urethane additive composition.
Description
본 발명은 폴리우레탄 폼 발포시 발생되는 스코칭 현상을 효과적으로 억제하기 위한 폴리우레탄 첨가제 조성물 및 그 제조방법에 관한 것이다. 보다 구체적으로, 본 발명은 용매에 힌더드페놀계, 방향족아민계 및 포스파이트계 산화방지제를 혼합 및 중합시켜 폴리우레탄 폼 발포시 열안정성이나 스코칭 현상 억제 효과를 갖게 하는 폴리우레탄 첨가제 조성물 및 그 제조방법에 관한 것이다.
The present invention relates to a polyurethane additive composition and a method for producing the same for effectively suppressing the scouring phenomenon generated during polyurethane foam foaming. More specifically, the present invention is a polyurethane additive composition and a hindered phenol-based, aromatic amine-based and phosphite-based antioxidants in the solvent to mix and polymerize to have a thermal stability or the effect of inhibiting the scoping phenomenon when foaming polyurethane foam and its It relates to a manufacturing method.
폴리우레탄 폼 제품은 단열성, 흡음성, 탄성 등이 우수하여 건축 또는 산업용 단열제, 강당 등의 흡음제, 가구용 침대 및 소파, 자동차산업 등에 광범위하게 사용되고 있다. Polyurethane foam products have excellent thermal insulation, sound absorption, elasticity, etc., and are widely used in building or industrial insulation, sound absorbers such as auditoriums, furniture beds and sofas, and the automobile industry.
그러나 폴리우레탄 폼은 그 발포 반응시 폼 내부의 온도가 아주 높게(170 내지 180 ℃) 올라가며, 이 반응은 완료될 때까지 1일 이상의 상당시간 동안 지속된다. 이로 인해서, 폴리우레탄 폼 내부는 열화 또는 탄화되기 때문에, 황변 현상이 발생하는 등 폴리우레탄 폼 전체의 물성은 변하게 되고, 폴리우레탄 폼 내부는 발화를 유발시켜 대형 화재를 일으킬 수 있다.However, polyurethane foams have a very high temperature (170 to 180 ° C.) inside the foam during the foaming reaction, and the reaction lasts for a significant time of more than one day until completion. For this reason, since the inside of the polyurethane foam is deteriorated or carbonized, physical properties of the entire polyurethane foam, such as a yellowing phenomenon, are changed, and the inside of the polyurethane foam may cause ignition and cause a large fire.
다시 말해서, 발포 반응시 폴리우레탄 폼 내부의 온도가 상승하여 고열이 발생하게 되면, 이 열에 의해 폴리우레탄 폼 제품에 황변 현상(스코칭 현상)이 발생하게 되고, 더 심할 경우에는 폴리우레탄 폼 제품이 탄화에 의해 발화되어 대형화재로 발전한다.In other words, if the temperature inside the polyurethane foam rises during the foaming reaction, and high heat is generated, the yellowing phenomenon (scoring phenomenon) occurs in the polyurethane foam product by this heat. It is ignited by carbonization and develops into a large fire.
한편, 폴리우레탄 폼이 그 내부의 고열로 인해 발화되면, 폴리우레탄 폼의 특성상 소화전의 고압의 물이나 소화기를 내부까지 침투시킬 수 없어, 폴리우레탄 폼이 전소될 때까지 기다리는 수밖에 없다.On the other hand, when the polyurethane foam is ignited due to the high temperature therein, due to the characteristics of the polyurethane foam can not penetrate the high-pressure water or fire extinguishers inside, there is no choice but to wait until the polyurethane foam burns out.
특히 최근 들어서, 폴리우레탄 폼 제조업체들은 폴리우레탄 폼 제품의 단가 경쟁력을 위해 원료비가 적게 드는 저밀도 제품을 많이 생산하고 있으며, 이 저밀도 폴리우레탄 폼을 제조하기 위해 주원료인 폴리올의 일정성분으로서 발포 기능 및 폴리올 기능을 하는 물(H2O)을 많이 사용하게 된다. 물을 사용하지 않으면, 생산단가가 상승됨은 물론이고, 생산성과 수율 문제로 인해 발포 폼 블록의 폭과 높이를 줄이거나 낮춰야하기 때문에, 다양하게 제품을 생산해낼 수 없다. 하지만 물을 사용하게 되면, 우레탄 폼 생산 공정에서 물과 이소시아네이트가 반응하게 되어 내부 발열이 많아져 폴리우레탄 폼 내의 중앙부에 스코치 현상(열노화로 인한 황변 현상)이 나타나게 되는 문제점이 발생한다.In particular, in recent years, polyurethane foam manufacturers are producing a lot of low-density products with low raw material costs for the cost competitiveness of polyurethane foam products, foaming function and polyol as a constant component of the polyol, the main raw material for manufacturing the low-density polyurethane foam It will use a lot of water (H 2 O) to function. If water is not used, production costs will rise, and productivity and yield issues will have to reduce or decrease the width and height of the foam foam block, thus making it impossible to produce a variety of products. However, when water is used, water and isocyanate react in the urethane foam production process, and the internal heat generation increases, causing a scorch phenomenon (yellowing due to thermal aging) to appear in the center of the polyurethane foam.
게다가, 최근에 자동차, 건축용, 산업 용도의 폴리우레탄 폼의 난연성 문제가 대두되면서, 폴리우레탄 폼 생산시 난연제를 첨가하게 되는데, 이때 주로 사용되는 난연제는 저독성 또는 무독성 특성을 갖는 유기 난연제로서 스코치 현상에 악영향을 끼치며, 특히 인계 또는 염소계 난연제는 스코치 현상(탄화 현상)을 더욱 악화시킨다.In addition, in recent years, the problem of flame retardancy of polyurethane foam for automobile, construction, and industrial use has been added, flame retardant is added in the production of polyurethane foam, which is mainly used as an organic flame retardant with low toxicity or non-toxic properties to scorch phenomenon It adversely affects, in particular phosphorus- or chlorine-based flame retardants further exacerbate the scorch phenomenon (carbonization).
따라서 폴리우레탄 폼 연속 블록 생산업체는, 폴리우레탄 폼 내부의 고열을 흡수하거나 낮춰줄 수 있는 근본적인 처방을 하지 않는다면, 항상 대형화재의 위험에 노출될 수밖에 없으며, 이런 이유와 빈번한 화재로 인해 화재보험회사가 책정하는 화재보험 적용비율이 제일 높은 업체에 속하며, 화재보험회사로부터 화재보험가입을 기피당하는 업종에 속해 있다.Therefore, polyurethane foam continuous block producers are always exposed to the risk of large fires unless they have a fundamental prescription to absorb or lower the high temperature inside the polyurethane foam. It belongs to the company with the highest rate of fire insurance coverage, and is in the industry which is avoided by fire insurance company.
이에 따라, 상기와 같은 문제점을 해결하기 위해서 열안정제 또는 변성 폴리올 첨가, 발포 공정 및 환경 개선 등을 비롯한 많은 연구가 진행되어 왔으며, 본 발명자는 용매에 힌더드페놀계, 방향족아민계 및 포스파이트계 산화방지제를 혼합 및 중합시켜, 폴리우레탄 폼 생산시 발생하는 고열에 대한 안정성이 매우 우수하고, 열을 흡수하는 기능이 우수하고, 시너지 효과가 나타나고, 폴리올 및 다른 원료와의 상용성이 우수한 폴리우레탄 첨가제 조성물을 개발하기에 이른 것이다.
Accordingly, in order to solve the above problems, many studies have been conducted including addition of a thermal stabilizer or modified polyol, foaming process and environmental improvement, and the present inventors have used hindered phenol-based, aromatic amine-based, and phosphite-based solvents. By mixing and polymerizing antioxidant, it has very good stability against high heat generated in polyurethane foam production, excellent heat absorption function, synergistic effect, and excellent compatibility with polyol and other raw materials. It is early to develop an additive composition.
본 발명의 목적은 폴리우레탄 폼 발포시 발열반응으로 인해 발생되는 폼의 황변 현상을 억제하고 화재를 방지하거나 지연시키는 효과가 우수한 폴리우레탄 첨가제 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a polyurethane additive composition excellent in the effect of inhibiting the yellowing of the foam caused by the exothermic reaction upon foaming polyurethane foam and preventing or delaying the fire.
본 발명의 또 다른 목적은 폴리우레탄 폼의 원료 중 열에 약한 원료 성분에 대해 우수한 내열성을 부여하여 여러 기능을 가진 원료들을 쉽게 혼합할 수 있게 해주어, 기능이 다양한 폴리우레탄 폼 제품의 생산을 가능하게 해주는 폴리우레탄 첨가제 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide excellent heat resistance to the raw material components of the weak heat of the polyurethane foam to make it easy to mix the raw materials having a variety of functions, enabling the production of a variety of functional polyurethane foam products It is to provide a polyurethane additive composition.
본 발명의 다른 목적은 폴리우레탄 발포과정에서 사용되는 착색제(Colorant)의 탈색 및 변색을 방지하거나 개선하기 위한 폴리우레탄 첨가제 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a polyurethane additive composition for preventing or improving discoloration and discoloration of a colorant used in a polyurethane foaming process.
본 발명의 또 다른 목적은 아주 낮은 점도의 액상으로 되어 있어 주원료인 폴리올과 상용성이 좋고, 부원료와의 혼합성이 우수하며, 사용하기에 편리한 폴리우레탄 첨가제 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a polyurethane additive composition which is a liquid having a very low viscosity and has good compatibility with a polyol which is a main raw material, excellent compatibility with secondary raw materials, and which is convenient to use.
본 발명의 또 다른 목적은 스코칭 현상뿐만 아니라, 산화방지성, UV 안정성 등의 시너지 효과가 있는 폴리우레탄 첨가제 조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide a polyurethane additive composition having synergistic effects such as oxidation resistance, UV stability, as well as scouring phenomenon.
본 발명의 또 다른 목적은 폴리우레탄 폼 발포시 발생되는 황변 현상을 억제하고 화재를 방지하거나 지연시키는 효과가 있는 폴리우레탄 첨가제 조성물의 제조방법을 제공하기 위한 것이다.Still another object of the present invention is to provide a method for preparing a polyurethane additive composition which has an effect of inhibiting yellowing and preventing or delaying fire caused by polyurethane foam foaming.
본 발명의 상기 및 기타의 목적들은 모두 하기 설명되는 본 발명에 의해서 모두 달성될 수 있다. 이하 본 발명의 내용을 하기에 상세히 설명한다.
The above and other objects of the present invention can all be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.
본 발명은 용매 5 내지 30 중량%, 힌더드 페놀계 산화방지제 5 내지 20 중량%, 방향족 아민계 산화방지제 10 내지 40 중량%, 및 포스파이트계 산화방지제 30 내지 80 중량%를 포함하는 폴리우레탄 첨가제 조성물을 제공한다.Polyurethane additive comprising 5 to 30% by weight of solvent, 5 to 20% by weight of hindered phenolic antioxidant, 10 to 40% by weight of aromatic amine antioxidant, and 30 to 80% by weight of phosphite antioxidant To provide a composition.
또한 본 발명은 수분이 제거된 반응조에 용매 5 내지 30 중량% 및 액상의 포스파이트계 산화방지제 30 내지 80 중량%를 투입하여 온도를 50 내지 100 ℃ 까지 올리면서 교반하고, 그리고 상기 반응조에 힌더드 페놀계 산화방지제 5 내지 20 중량% 및 방향족 아민계 산화방지제 10 내지 40 중량%를 투입하여 용해시킨 후 온도를 50 내지 100 ℃ 유지시키면서 60 내지 200 분 동안 중합하는 단계로 제조되는 폴리우레탄 첨가제 조성물의 제조방법을 제공한다.
In another aspect, the present invention by adding 5 to 30% by weight of the solvent and 30 to 80% by weight of the liquid phosphite-based antioxidant in the reaction tank is removed while stirring while raising the temperature to 50 to 100 ℃, and hindered in the reactor 5 to 20% by weight of a phenolic antioxidant and 10 to 40% by weight of an aromatic amine antioxidant were dissolved, followed by polymerization for 60 to 200 minutes while maintaining a temperature of 50 to 100 ℃ of the polyurethane additive composition It provides a manufacturing method.
본 발명에 따른 폴리우레탄 첨가제 조성물은 폴리우레탄 폼 발포시 발생되는 스코칭 현상을 개선시킬 수 있고, 주원료, 부원료와의 상용성이 우수하고, 산화방지제, UV 안정제 및 열안정제와의 상용성이 우수하여 이로 인해 시너지 효과를 낼 수 있다.
Polyurethane additive composition according to the present invention can improve the scouring phenomenon generated during polyurethane foam foam, excellent compatibility with the main raw materials, secondary raw materials, excellent compatibility with antioxidants, UV stabilizers and thermal stabilizers This can lead to synergies.
본 발명에 따른 폴리우레탄 첨가제 조성물은 용매 5 내지 30 중량%, 힌더드 페놀계 산화방지제 5 내지 20 중량%, 방향족 아민계 산화방지제 10 내지 40 중량% 및 포스파이트계 산화방지제 30 내지 80 중량%로 이루어진다.Polyurethane additive composition according to the present invention is 5 to 30% by weight solvent, 5 to 20% by weight hindered phenolic antioxidant, 10 to 40% by weight aromatic amine antioxidant and 30 to 80% by weight phosphite antioxidant Is done.
본 발명의 일 실시예에서, 상기 용매는 메틸에틸케톤, N-메틸피롤리돈(NMP), N-에틸피롤리돈(NEP), 메틸카비톨, 아미드계 용제 등에서 선택되며, 상기 용매로서 N-메틸피롤리돈(NMP)을 사용하는 것이 바람직하고, 상기 용매를 5 내지 30 중량%의 함량 범위로 사용하는 것이 바람직하다.In one embodiment of the present invention, the solvent is selected from methyl ethyl ketone, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), methyl carbitol, amide solvents, etc., N as the solvent Preference is given to using -methylpyrrolidone (NMP), preferably from 5 to 30% by weight of the solvent.
본 발명의 일 실시예에서, 상기 힌더드 페놀계 산화방지제는 펜타에리스리톨테트라키스(3-(3,5-디-터셔리부틸-4-히드록시페닐)프로피오네이트), 옥타데실-3-(3,5-디-터셔리부틸-4-히드록시페닐)프로피오네이트, 에틸렌비스(옥시에틸렌)비스-(3-(5-터셔리부틸-4-히드록시-m-토릴)-프로피오네이트), 프로피오네이트(C2H5COO)를 포함하는 힌더드 페놀계 산화방지제 등에서 선택되며, 상기 힌더드 페놀계 산화방지제로서 펜타에리스리톨테트라키스(3-(3,5-디-터셔리부틸-4-히드록시페닐)프로피오네이트)를 사용하는 것이 바람직하고, 상기 힌더드 페놀계 산화방지제를 5 내지 20 중량%의 함량 범위로 사용하는 것이 바람직하다.In one embodiment of the present invention, the hindered phenolic antioxidant is pentaerythritol tetrakis (3- (3,5-di-tertbutylbutyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis- (3- (5-tert-butyl-4-hydroxy-m-tolyl) -prop Cationate), and a hindered phenolic antioxidant including propionate (C 2 H 5 COO) and the like, and pentaerythritol tetrakis (3- (3,5-di-ter) as the hindered phenolic antioxidant. Sherylbutyl-4-hydroxyphenyl) propionate), and it is preferable to use the hindered phenolic antioxidant in a content range of 5 to 20% by weight.
본 발명의 일 실시예에서, 상기 방향족 아민계 산화방지제는 4,4’-비스(α,α-디메틸벤질)디페닐아민, N-N’-디페닐-p-페닐렌디아민, N-페닐-1-나프틸아민 등에서 선택되며, 상기 방향족 아민계 산화방지제로서 4,4’-비스(α,α-디메틸벤질)디페닐아민을 사용하는 것이 바람직하고, 상기 방향족 아민계 산화방지제를 10 내지 40 중량%의 함량 범위로 사용하는 것이 바람직하다.In one embodiment of the present invention, the aromatic amine antioxidant is 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, N-N'-diphenyl-p-phenylenediamine, N-phenyl It is selected from -1-naphthylamine and the like, and it is preferable to use 4,4'-bis (α, α-dimethylbenzyl) diphenylamine as the aromatic amine antioxidant, and the aromatic amine antioxidant is 10 to It is preferable to use in the content range of 40% by weight.
본 발명의 일 실시예에서, 상기 포스파이트계 산화방지제는 테트라페닐디프로필렌글리콜디포스파이트, 디페닐이소데실포스파이트, 디페닐이소옥틸포스파이트, 4,4’-부틸리덴비스(3-메틸-6-터셔리부틸페닐)-디트리데실포스파이트, 디이소데실펜타에리스리톨테트라포스파이트 등에서 선택되며, 상기 포스파이트계 산화방지제로서 테트라페닐디프로필렌글리콜디포스파이트를 사용하는 것이 바람직하고, 상기 포스파이트계 산화방지제를 30 내지 80 중량%의 함량 범위로 사용하는 것이 바람직하다. In one embodiment of the present invention, the phosphite-based antioxidant is tetraphenyldipropylene glycol diphosphite, diphenylisodecyl phosphite, diphenyl isooctyl phosphite, 4,4'- butylidenebis (3-methyl -6-tertarybutylphenyl) -ditridecyl phosphite, diisodecyl pentaerythritol tetraphosphite, and the like, and it is preferable to use tetraphenyldipropylene glycol diphosphite as the phosphite-based antioxidant, Pytic antioxidants are preferably used in the content range of 30 to 80% by weight.
본 발명에 따른 폴리우레탄 첨가제 조성물은 폴리우레탄 폼의 원료 중 열에 약한 원료 성분에 대해 우수한 내열성을 부여하여 여러 기능을 가진 원료들을 쉽게 혼합할 수 있게 해주며, 이로써 기능이 다양한 폴리우레탄 폼 제품의 생산을 가능하게 할 수 있다.The polyurethane additive composition according to the present invention provides excellent heat resistance to raw material components that are weak to heat among the raw materials of the polyurethane foam, thereby making it possible to easily mix raw materials having various functions, thereby producing various polyurethane foam products. Can be enabled.
본 발명에 따른 폴리우레탄 첨가제 조성물은 폴리우레탄 폼 발포시 사용되는 착색제(Colorant)의 탈색 및 변색을 방지하거나 개선할 수 있다.Polyurethane additive composition according to the present invention can prevent or improve the discoloration and discoloration of the colorant (Colorant) used in the polyurethane foam foam.
본 발명에 따른 폴리우레탄 첨가제 조성물은 아주 낮은 점도의 액상으로 되어 있어, 주원료인 폴리올과 상용성이 좋고, 부원료와의 혼합성이 우수하며, 사용하기에 편리하다.The polyurethane additive composition according to the present invention is a liquid having a very low viscosity, so that it is compatible with the polyol which is the main raw material, has excellent compatibility with the secondary raw materials, and is convenient for use.
본 발명의 일 실시예에서, 폴리우레탄 첨가제 조성물은, 폴리우레탄 폼의 산화방지제, UV 안정제, 열안정제 등과 같은 첨가제들을 더 포함할 수 있으며, 이들 첨가제들과의 상용성이 매우 우수하여 시너지 효과를 낼 수 있다. 다시 말해서, 본 발명에 따른 폴리우레탄 첨가제 조성물은, 폴리우레탄 폼 발포시 발생되는 황변 현상을 개선할 뿐만 아니라, 폴리우레탄 폼의 산화방지성, UV 안정성(내후성) 등을 개선할 수 있다.In one embodiment of the present invention, the polyurethane additive composition may further include additives such as antioxidants, UV stabilizers, heat stabilizers, etc. of the polyurethane foam, and has excellent synergistic effects with these additives. I can make it. In other words, the polyurethane additive composition according to the present invention may not only improve the yellowing phenomenon generated when the polyurethane foam is foamed, but also improve the antioxidant property, UV stability (weather resistance) and the like of the polyurethane foam.
본 발명의 일 실시예에서, 상기 산화방지제로서 벤젠프로파노익산 또는 3,5-비스(1,1-디메틸-에틸)-4-히드록시-C7-C9 가지형 알킬 에스테르를 사용하는 것이 바람직하고, UV안정제로서 에틸 4-[[(메틸페닐아미노)메틸렌]아미노]벤조에이트를 사용하는 것이 바람직하다. 열안정제의 예로는 디페닐 이소데실 포스파이트가 사용될 수 있다. In one embodiment of the present invention, it is preferable to use benzenepropanoic acid or 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-C 7 -C 9 type alkyl ester as the antioxidant. It is preferable to use ethyl 4-[[(methylphenylamino) methylene] amino] benzoate as the UV stabilizer. Diphenyl isodecyl phosphite may be used as an example of the heat stabilizer.
본 발명에 따른 폴리우레탄 첨가제 조성물 제조방법은 수분이 제거된 반응조에 용매 5 내지 30 중량% 및 액상의 포스파이트계 산화방지제 30 내지 80 중량%를 투입하여 온도를 50 내지 100 ℃ 까지 올리면서 교반하고, 그리고 상기 반응조에 힌더드 페놀계 산화방지제 5 내지 20 중량% 및 방향족 아민계 산화방지제 10 내지 40 중량%를 투입하여 용해시킨 후 온도를 50 내지 100 ℃ 유지시키면서 60 내지 200 분 동안 중합하는 단계로 이루어진다.In the method for preparing a polyurethane additive composition according to the present invention, 5-30% by weight of a solvent and 30-80% by weight of a liquid phosphite-based antioxidant are added to a reaction tank from which water is removed while stirring while raising the temperature to 50-100 ° C. In addition, 5 to 20% by weight of the hindered phenolic antioxidant and 10 to 40% by weight of the aromatic amine antioxidant are dissolved in the reactor, followed by polymerization for 60 to 200 minutes while maintaining a temperature of 50 to 100 ° C. Is done.
본 발명에 따른 폴리우레탄 첨가제 조성 물질을 제조하기 위해서는 우선 반응조의 수분을 제거하여야 하며, 그 다음에 상기 반응조에 용매와 액상의 포스파이트계 산화방지제를 투입하여 온도를 50 내지 100 ℃까지 올리면서 교반한다. 용매와 액상 포스파이트계 산화방지제를 완전하게 혼합한 후에, 상기 반응조에 힌더드 페놀계 산화방지제와 방향족 아민계 산화방지제를 투입시킨다. 용매에 힌더드 페놀계 산화방지제와 방향족 아민계 산화방지제를 완전히 용해시킨 후에 온도를 50 내지 100 ℃로 유지시키면서 60 내지 200 분간 중합한다.
In order to prepare the polyurethane additive composition material according to the present invention, first, the water of the reaction tank must be removed, and then a solvent and a liquid phosphite-based antioxidant are added to the reaction tank, followed by stirring while raising the temperature to 50 to 100 ° C. do. After the solvent and the liquid phosphite-based antioxidant are completely mixed, a hindered phenol-based antioxidant and an aromatic amine-based antioxidant are added to the reactor. After completely dissolving the hindered phenolic antioxidant and the aromatic amine antioxidant in the solvent, the polymerization is carried out for 60 to 200 minutes while maintaining the temperature at 50 to 100 ° C.
본 발명은 하기의 실시예에 의해 보다 구체화될 것이나, 하기의 실시예는 본 발명을 예시하기 위한 목적으로 사용될 뿐이며 본 발명의 보호범위를 한정하고자 하는 것은 아니다.The present invention will be further illustrated by the following examples, which are used only for the purpose of illustrating the invention and are not intended to limit the scope of the invention.
실시예Example 1 One
수분이 제거된 반응조에, 용매인 N-메틸 피롤리돈(NMP) 16 중량부와 액상 포스파이트계 산화방지제인 테트라페닐 디프로필렌 글리콜 포스파이트 60 중량부를 투입하고 온도를 50 내지 100 ℃까지 올리면서 교반한다. 상기 반응조에 힌더드 페놀계 산화방지제인 펜타에리스리톨 테트라키스 (3-(3,5-디-터셔리부틸-4-히드록시페닐)프로피오네이트) 8 중량부와 방향족 아민계 산화방지제인 4,4’-비스(α,α-디메틸벤질) 디페닐아민 16 중량부를 투입하여 용해시킨다. 상기 반응조 온도를 50 내지 100 ℃로 유지시키면서 90 분간 중합반응을 시킨다. 반응 생성물로서 균일한 첨가제 조성물이 생성된다.In the reaction vessel from which water was removed, 16 parts by weight of N-methyl pyrrolidone (NMP) as a solvent and 60 parts by weight of tetraphenyl dipropylene glycol phosphite as a liquid phosphite-based antioxidant were added thereto, and the temperature was raised to 50 to 100 ° C. Stir. 8 parts by weight of pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), which is a hindered phenol-based antioxidant, and 4, which is an aromatic amine-based antioxidant, 16 parts by weight of 4'-bis (α, α-dimethylbenzyl) diphenylamine was added and dissolved. The polymerization reaction is conducted for 90 minutes while maintaining the temperature of the reactor at 50 to 100 ° C. As a reaction product a uniform additive composition is produced.
실시예 1에 따라 제조된 폴리우레탄 첨가제 조성물의 물성을 하기 표 1에 나타내었다.
Physical properties of the polyurethane additive composition prepared according to Example 1 are shown in Table 1 below.
실시예Example 2 2
스코칭 현상 개선 정도를 나타내기 위하여 폴리에테르폴리올 80.0 중량부, 폴리머폴리올 20.0 중량부, 물 4.5 중량부, 난연제(다이하치사의 CR-530) 13.0 중량부, 메틸클로라이드(MC) 8.0 중량부, 아민 촉매 0.1 중량부, 실리콘 정포제 1.6 중량부, 톨루엔 디이소시아네이트 55.0 중량부 및 상기 실시예 1에 따라 제조된 폴리우레탄 첨가제 조성물을 사용하여, 폴리우레탄 첨가제 조성물의 함량을 변화시키면서 발포 실험을 진행하였다.80.0 parts by weight of polyether polyol, 20.0 parts by weight of polymer polyol, 4.5 parts by weight of water, 13.0 parts by weight of flame retardant (CR-530 from Daihachi), 8.0 parts by weight of methyl chloride (MC) Foaming experiment was carried out while varying the content of the polyurethane additive composition using 0.1 parts by weight of the amine catalyst, 1.6 parts by weight of the silicone foam stabilizer, 55.0 parts by weight of toluene diisocyanate and the polyurethane additive composition prepared according to Example 1. .
상기 실시예 1의 폴리우레탄 첨가제 조성물을 각각 0 중량부, 0.5 중량부, 1.0 중량부, 1.5 중량부 사용한 폼을 발포하여, 버블타임 직후에 바로 그 폼을 전자레인지에 1 분 30 초간 돌려 꺼낸 뒤 폼 중앙부의 스코칭 면적을 측정하였으며, 측정 결과는 하기 표 2에 나타내었다.After foaming foams using 0 parts by weight, 0.5 parts by weight, 1.0 parts by weight and 1.5 parts by weight of the polyurethane additive composition of Example 1, the foam was immediately taken out of the microwave oven for 1 minute and 30 seconds immediately after the bubble time. The scouring area of the center of the foam was measured, and the measurement results are shown in Table 2 below.
상기 표 2를 보면, 본 발명에 따른 폴리우레탄 첨가제 조성물을 사용한 경우에 사용하지 않았을 때와 비교하여 폼의 스코칭 현상이 훨씬 개선되었음을 알 수 있다.
Looking at Table 2, it can be seen that the scouring phenomenon of the foam is much improved compared to when not used when using the polyurethane additive composition according to the present invention.
실시예Example 3 3
본 발명에 따른 첨가제 조성물을 사용한 경우와 사용하지 않은 경우의 시간 경과에 따른 산화방지 효과에 관한 결과를 표 3에 나타내었다. 실시예 3은 실시예 1에 따른 폴리우레탄 첨가제 조성물을 산화방지제와 함께 사용한 폼을 발포한 것이고, 비교실시예는 실시예 1에 따른 폴리우레탄 첨가제 조성물을 사용하지 않고 산화방지제만 사용한 폼을 발포한 경우이다. 하기 표 3의 백색지수와 황색지수 데이터는 폼을 발포한 뒤 이를 바로 재단하여 측색기로 측정한 초기데이터와 이 폼을 실험실에서 14 일 동안 자연 노출 방치시킨 뒤 다시 측색기로 측정한 데이터를 측정한 값이다.
Table 3 shows the results of the antioxidant effect over time with and without the additive composition according to the present invention. Example 3 is foamed foam using the polyurethane additive composition according to Example 1 with the antioxidant, Comparative Example foamed foam using only the antioxidant without using the polyurethane additive composition according to Example 1 If it is. The white index and yellow index data of Table 3 are measured by measuring the color data after foaming the foam immediately after foaming, and leaving the form in the laboratory for 14 days, and then measuring the data measured by the color measuring instrument again. to be.
상기 표 3을 보면, 본 발명에 따른 폴리우레탄 폼 첨가제 조성물을 산화방지제와 함께 사용한 경우에 스코칭 현상뿐만 아니라, 변색성도 함께 개선되었음을 알수 있다.
Looking at Table 3, it can be seen that not only the scouring phenomenon, but also discoloration when the polyurethane foam additive composition according to the present invention is used together with the antioxidant.
본 발명의 단순한 변형 내지 변경은 이 분야에 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
Claims (7)
힌더드 페놀계 산화방지제 5 내지 20 중량%;
방향족 아민계 산화방지제 10 내지 40 중량%; 및
포스파이트계 산화방지제 30 내지 80 중량%;
를 포함하는 것을 특징으로 하는 폴리우레탄 첨가제 조성물.
5 to 30 wt% solvent;
5 to 20% by weight of hindered phenolic antioxidants;
10 to 40 wt% of aromatic amine antioxidants; And
30 to 80% by weight of phosphite-based antioxidants;
Polyurethane additive composition comprising a.
The method of claim 1, wherein the solvent is selected from the group consisting of methyl ethyl ketone, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), methyl carbitol and amide solvents Polyurethane additive composition.
The method of claim 1, wherein the hindered phenolic antioxidant is pentaerythritol tetrakis (3- (3,5-di-tertbutylbutyl-4-hydroxyphenyl) propionate), octadecyl-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis- (3- (5-tert-butylbutyl-hydroxy-m-tolyl) -propionate And a hindered phenol-based antioxidant comprising propionate (C 2 H 5 COO).
The compound according to claim 1, wherein the aromatic amine antioxidant is 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, N-N'-diphenyl-p-phenylenediamine, and N-phenyl- Polyurethane additive composition, characterized in that it is selected from the group consisting of 1-naphthylamine.
The method of claim 1, wherein the phosphite-based antioxidant is tetraphenyldipropylene glycol diphosphite, diphenylisodecyl phosphite, diphenyl isooctyl phosphite, 4,4'-butylidene bis (3-methyl-6 Polyurethane butylphenyl) -ditridecyl phosphite and diisodecyl pentaerythritol tetraphosphite.
The polyurethane additive composition of claim 1, wherein the polyurethane additive composition further comprises an antioxidant, a UV stabilizer, a heat stabilizer, or a mixture thereof.
상기 반응조에 힌더드 페놀계 산화방지제 5 내지 20 중량% 및 방향족 아민계 산화방지제 10 내지 40 중량%를 투입하여 용해시킨 후 온도를 50 내지 100 ℃ 유지시키면서 60 내지 200 분 동안 중합하는;
단계로 제조되는 것을 특징으로 하는 폴리우레탄 첨가제 조성물 제조방법.5 to 30% by weight of a solvent and 30 to 80% by weight of a liquid phosphite-based antioxidant were added to a reaction tank from which water was removed, followed by stirring while raising the temperature to 50 to 100 ° C; And
5 to 20% by weight of the hindered phenolic antioxidant and 10 to 40% by weight of the aromatic amine antioxidant were dissolved in the reactor, followed by polymerization for 60 to 200 minutes while maintaining the temperature at 50 to 100 ° C;
Polyurethane additive composition manufacturing method characterized in that it is prepared in a step.
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| KR1020100077690A KR101181253B1 (en) | 2010-08-12 | 2010-08-12 | Polyurethane Additive Composition for Suppressing the Scorching Phenomenon Occurred When Polyurethane Foam is Discharged and Method for Preparing the Same |
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| KR1020100077690A KR101181253B1 (en) | 2010-08-12 | 2010-08-12 | Polyurethane Additive Composition for Suppressing the Scorching Phenomenon Occurred When Polyurethane Foam is Discharged and Method for Preparing the Same |
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| TWI743183B (en) * | 2016-08-30 | 2021-10-21 | 巴地斯顏料化工廠 | A liquid antioxidant composition for raw rubbers |
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| CN108017766B (en) * | 2016-11-01 | 2020-12-01 | 中国石油化工集团公司 | Composite antioxidant for preventing or reducing reddening of polyurethane soft foam and application thereof |
| CN114481624B (en) * | 2022-02-08 | 2024-05-03 | 东莞市中纺化工有限公司 | Anti-yellowing additive and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001081674A (en) * | 1999-09-14 | 2001-03-27 | Asahi Kasei Corp | Finishing lubricant for elastic fiber |
| JP2008208264A (en) * | 2007-02-27 | 2008-09-11 | Inoac Corp | Soft polyurethane foam |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001081674A (en) * | 1999-09-14 | 2001-03-27 | Asahi Kasei Corp | Finishing lubricant for elastic fiber |
| JP2008208264A (en) * | 2007-02-27 | 2008-09-11 | Inoac Corp | Soft polyurethane foam |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI743183B (en) * | 2016-08-30 | 2021-10-21 | 巴地斯顏料化工廠 | A liquid antioxidant composition for raw rubbers |
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