KR101766439B1 - Manufacturing method of bio-polyurethane and polyurethane manufacturing thereof and polyurethane coating fiber coating polyurethane thereof - Google Patents
Manufacturing method of bio-polyurethane and polyurethane manufacturing thereof and polyurethane coating fiber coating polyurethane thereof Download PDFInfo
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- KR101766439B1 KR101766439B1 KR1020150091424A KR20150091424A KR101766439B1 KR 101766439 B1 KR101766439 B1 KR 101766439B1 KR 1020150091424 A KR1020150091424 A KR 1020150091424A KR 20150091424 A KR20150091424 A KR 20150091424A KR 101766439 B1 KR101766439 B1 KR 101766439B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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Abstract
(A1) 20 to 40% by weight of a synthetic polyol having a weight average molecular weight of 1800 to 2200 Mw and an OH value of 30 to 90 mgKOH / g, (a2) a weight average molecular weight of 1800 to 2200 Mw (A3) 20 to 50% by weight of polyethylene glycol having a weight average molecular weight of 400 to 4000 and (a4) 20 to 50% by weight of ethylene glycol 3 to 50% by weight of a polyol having a hydroxyl value of 45 to 180 mg / And 20 to 200 parts by weight of an isocyanate (B) to 100 parts by weight of a polyhydric alcohol composition (A) containing 5 to 5% by weight of a polyol.
Description
The present invention relates to a bio-polyurethane, a process for producing the same, a polyurethane produced therefrom, and a polyurethane-coated fiber coated therewith.
Specifically, the use of petroleum-based raw material (synthetic polyol), which is a limited resource, is inhibited and polyurethane resin is produced by using natural resources such as vegetable oil, which is a renewable resource, Moisture permeability and the like, a process for producing the same, and a bio-polyurethane-coated bio-polyurethane coated fiber produced therefrom.
Polyurethanes are collectively referred to as polymer compounds containing urethane bonds. They react with alcohols having at least one isocyanate group (-NCO) and at least one active hydroxyl group (-OH) under proper conditions to form a urethane bond (-NHCOO-) Generally, a polymer having a molecular weight of 1,000 or more is referred to as polyurethane.
Meanwhile, the US barrel oil price in 1997 increased fourfold from US $ 23 to US $ 98 per barrel in August 2011 and reached a record high of US $ 134 / bbl in July 2008. Because polyol and isocyanate, which are the main raw materials of polyurethane (PU), are manufactured based on petroleum, rising prices of crude oil are affecting the price increase of PU products.
Also continues the requirement about replacement to the worldwide vegetable oil renewable petroleum-based raw materials in the polymer materials production, focusing on the environmental point of view, and particularly in February 2005 as the Kyoto Protocol enters into force industrialized countries, the CO 2 There was an obligation to reduce the same greenhouse gas. In particular, Korea is the ninth largest producer of CO 2 in the world, and it is expected that the demand of the international society for greenhouse gas reduction will increase, and the additional cost is also affecting the price increase of PU products.
As a result of this rise in crude oil prices and the strengthening of environmental regulations, the need to replace petroleum-based polyurethane raw materials with renewable resources has been raised.
Prior arts for bio polyols used in bio-polyurethane are disclosed in Korean Patent No. 10-1468070, which comprises hydrolyzing animal and plant oils to prepare free fatty acids, preparing dimer acid using the free fatty acids, Is reacted with an epoxy to prepare a diol, and conducting the reaction at a high temperature and a high pressure using isocyanate. However, the rigid polyurethane foam to which the biopolyol is applied has a low compressive strength, tensile strength, and impact resistance due to low storage stability and functional groups of the biopolyol, which limits application to hard polyurethane foam used as an LNG insulator . In addition, the biopolyol has poor reactivity during the production of rigid polyurethane foam, and it is impossible to produce a polyurethane which is satisfactory in terms of physical properties.
Korean Patent Laid-Open Publication No. 10-2014-0114676A also discloses a bio-polyol made from castor oil or soybean oil mainly used as a food resource. However, sufficient physical properties are not guaranteed for application to rigid polyurethane, and the amount of bio- It is difficult to use more than% and it is insufficient in terms of environmental friendliness.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a novel bio polyurethane which can use a high amount of bio polyol in order to improve disadvantages of use of low bio poly It is another object of the present invention to provide a method for producing the same and a fiber coated with bio-polyurethane produced therefrom.
Another object of the present invention is to provide a bio-polyurethane-coated fiber coated with bio-polyurethane having the above properties, and to provide polyurethane fiber having excellent moisture permeability, water pressure and peel strength.
(A1) 20 to 40% by weight of a synthetic polyol having a weight average molecular weight of 1,800 to 2,200 Mw and an OH value of 30 to 90 mgKOH / g, (a2) (A3) 20 to 50% by weight of a polyethylene glycol having a weight average molecular weight of 400 to 4000, (b) a polyol having a weight average molecular weight of 1,800 to 2,200 Mw and a hydroxyl value of 45 to 180 mgKOH / g, And (a4) 20 to 200 parts by weight of an isocyanate (B) to 100 parts by weight of a polyhydric alcohol composition (A) containing 3 to 5% by weight of ethylene glycol.
In the present invention, the composition ratio of the polyhydric alcohol composition (A) and the isocyanate (B) component is preferably 1: 0.8 to 1.2, but is not limited thereto. And 20 to 200 parts by weight of isocyanate (B) may be used, but this is more preferable when the above-mentioned equivalent ratio is satisfied.
In the present invention, the polyethylene glycol may have a weight average molecular weight of 100 to 4,000, more specifically, 1 to 99% by weight of polyethylene glycol having a weight average molecular weight of less than 100 to 1,000 and 1 to 99% by weight of polyethylene glycol having a weight average molecular weight of 1,000 to 4,000 %. ≪ / RTI >
In the present invention, the bio-polyol may be one prepared by modifying one or more selected from castor oil, soybean oil, seed oil, woody biomass, and waste glycerol.
Another aspect of the present invention is a polyurethane-coated polyurethane-coated fiber produced by the above production method, wherein the coating fiber has a peel strength of 2 (measured by a peel strength test according to KS K 0533 Wherein the water vapor permeability is 5,000 g / m < 2 > / day or more and the water pressure is 1,000 mm < 2 >
The bio-polyurethane resin produced according to the present invention may contain at least 25% by weight of bio-polyol in the total polyol composition, and even if the bio-polyol content is increased, the peel strength measured by KS K 0533 is not less than 2 N / It is possible to guarantee a water permeability of 5,000 g / m < 2 > / day or more and a water pressure of 1,000 mm < 2 > And can be applied to various functional fiber fabrics without deterioration of physical properties such as generation of precipitates, lowering of transparency, lowering of adhesive strength and lowering of water pressure.
Hereinafter, the method for producing a bio-polyurethane according to the present invention will be described in more detail. It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.
Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As used herein, the term "polyol" means an organic molecule having a hydroxy group per molecule with an average greater than 1.0.
The term "polyurethane foam" as used in the present invention means a cell structure obtained by reacting a di- or polyisocyanate with an isocyanate-reactive hydrogen-containing compound (polyol, amino alcohol and / or polyamine) and a blowing agent Quot; cellular foamed product ".
As used herein, the term "hydroxyl number" is an index indicating the amount of reactive hydroxyl groups that can participate in the reaction. The number of mg of KOH required to neutralize the acetic acid bonded to the acetyl compound obtained from 1 g of polyol (Unit: mgKOH / g).
As used herein, the term "acid number" means the number of mg of KOH required to neutralize the acid present in 1 g of the polyol sample (unit: mg KOH / g).
(A1) 20 to 40% by weight of a synthetic polyol having a weight average molecular weight of 1,800 to 2,200 Mw and an OH value of 30 to 90 mgKOH / g, (a2) a polyol having a weight average molecular weight (A3) 20 to 50% by weight of polyethylene glycol having a weight average molecular weight of 400 to 4000, and (a4) 20 to 50% by weight of polyethylene glycol having a weight average molecular weight of 400 to 4000, ) And 20 to 200 parts by weight of isocyanate (B) relative to 100 parts by weight of the polyhydric alcohol composition (A) containing 3 to 5% by weight of ethylene glycol.
Hereinafter, the bio-polyurethane composition according to the present invention will be described in more detail.
(a1) a synthetic polyol
In the present invention, the synthetic polyol is a material forming a soft segment of a polyurethane. In general, the synthetic polyol refers to both polyether-based, polyester-based, and polycarbonate-based materials in the case of polyols. The synthetic polyol (a1) Glycols, bio-polyols, and polyols other than ethylene glycol.
Synthetic polyols that can be used in the present invention are not limited to the polyhydric alcohols that can be used in the production of bio-polyurethanes except for the exclusion of the above-mentioned alcohols, and may include, for example, polyesters, polycarbonates, etc. The present invention is not limited thereto.
Examples of the polyester system include polyethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene amipate glycol, polycaprolactone glycol, diols such as ethylene glycol, 1,3-propanediol, 1,4 Butanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol and mixtures thereof with dicarboxylic acids such as adipic acid , 1,9-nonanedioic acid, and 1,12-dodecanedioic acid, and the like.
Examples of the polycarbonate-based polymer include at least one selected from polybutylene carbonate glycol, polyhexamethylene carbonate glycol, polypentane-1,5-carbonate diol, polyhexane-1,6-carbonate diol, and the like .
In the present invention, the synthetic polyol may have a hydroxyl value of 30 to 90 mgKOH / g, and more preferably 50 to 60 mgKOH / g. When it is less than 30 mgKOH / g, it is difficult to induce the urethane bond due to the reaction with isocyanate, so that the molecular weight of the polyurethane may be lowered. When it exceeds 90 mgKOH / g, the gelation proceeds due to the rapid reaction, It can be difficult. However, in general, adhesiveness and water pressure resistance of bio-polyurethane coating fibers produced according to an increase in the viscosity of the reaction product tend to increase, so it is preferable to use a polyol satisfying the above range.
In the present invention, the synthetic polyol may have a weight average molecular weight of 1,800 to 2,200 Mw. If the weight average molecular weight is less than 1,800 Mw, the overall physical properties will be degraded. In particular, the physical properties of the water pressure and the peel strength may be deteriorated. When the water pressure exceeds 2,200 Mw, the water pressure and peel strength may have sufficient physical properties, but the moisture permeability may decrease.
In the present invention, the synthetic polyol may include 20 to 40% by weight of 100% by weight of the polyhydric alcohol composition (A). The ratio of the equivalents of the two raw materials to the equivalents of the isocyanate reacting with the synthetic polyol, which is the basis of the polyurethane polymerization, is important, and when the equivalent value is changed outside the range, the targeted properties are drastically reduced.
(a2) Biofuels derived from natural oils
The bio-polyol derived from natural herb is a polyhydric alcohol prepared on the basis of recycled resources such as natural oil without using petroleum-based raw materials, and can be produced on the basis of plant and animal oils. Polyol polyol, polyester polyol, . ≪ / RTI >
The animal or vegetable oil may be a natural oil, preferably a vegetable oil. Examples of the animal oil may include fish oil, small oil, lard, sheep oil and the like, and mixtures thereof. Examples of the vegetable oil include vegetable oils such as sunflower seed oil, canola oil, palm oil, corn oil, cottonseed oil, plain oil, flaxseed oil, safflower oil, oats oil, olive oil, palm oil, peanut oil, rape oil, Soybean oil, castor oil and the like, and more typically, soybean oil, castor oil, palm oil, and the like, and mixtures thereof. However, the present invention is not limited thereto.
For example, in the case of pizza hemp, it is the oil obtained by squeezing the seed of castor bean (Rucinus communis). The seed contains about 45% of this oil and has a higher oil content percentage than other seeds. The fat is made entirely of triester (triglyceride) structure of fatty acid and glycerin. Castor induction Similarly, it is characterized in that about 90% of the triesters or fatty acids of glycerin are composed of ricinoleic acid. The remainder may contain oleic acid, linoleic acid, and the like.
In the present invention, the bio-polyol can be produced through a hydroxylate reaction. For example, ESO (epoxidized soybean oil), methanol, and formic acid are slowly added to the reactor under the N 2 purge condition so as to sufficiently stir while paying attention to heat generation in the reactor. The mixture which has been stirred is subjected to a hydroxylate reaction, and the mixture is heated and maintained at a temperature of 40 to 80 캜 for 6.5 to 13 hours until a desired hydroxyl value is obtained. Upon reaching the target water level, the reduced pressure reaction and solvent recovery are carried out at 60 ° C. Thereafter, the solvent, unreacted raw material and water are removed through elevated temperature and high vacuum reaction at 120 ° C for 5 hours to prepare a bio-polyol.
In the present invention, the bio polyol preferably has a hydroxyl value of 45 to 180 mgKOH / g, more preferably 50 to 80 mgKOH / g. When the water value is less than 45 mg KOH / g, it is difficult to increase the molecular weight of the polyurethane. When the water value is more than 180 mg KOH / g, the crosslinking is accelerated due to a rapid reaction during production.
In the present invention, the bio polyol may be contained in an amount of 15 to 40% by weight of the whole composition. When the amount is less than 15% by weight, the content is less than 25% by weight of 100% by weight of the total polyurethane, which is the target of addition of the bio-polyol. When the content is more than 40% by weight, relative properties can not be secured. Thereby causing an excessive viscosity increase and causing a coating process failure.
(a3) Polyethylene glycol
The polyethylene glycol is a polymer resin that is polymerized in the main chain of polyurethane to ensure physical properties such as moisture permeability of the coated fiber to be produced. However, other polyethers other than the above-mentioned polyethylene glycols such as polytetramethylene ether glycol, polypropylene glycol, polyoxyethylene ether glycol, polyoxypropylene ether glycol, polytetramethylene ether-co-3-methyltetramethylene ether glycol And polytetramethylene ether-co-2,3-dimethyl-tetramethylene ether glycol, may be used instead of polyethylene glycol, but the present invention is not limited thereto.
In the present invention, the polyethylene glycol may have a weight average molecular weight of 400 to 4,000, and more preferably 400 to 2,000. When the weight-average molecular weight is less than 400, the weight-average molecular weight of the polyurethane is too low to lower the moisture-permeability. If the weight-average molecular weight is more than 4,000, polyethylene glycol may be precipitated after the production, and the amount of isocyanate may be relatively increased, have.
In the present invention, the polyethylene glycol preferably contains 1 to 99% by weight of polyethylene glycol having a weight average molecular weight of less than 100 to 1,000 and 1 to 99% by weight of polyethylene glycol having a weight average molecular weight of 1,000 to 4,000, 40 to 60% by weight of a polyethylene glycol having a molecular weight of 100 to less than 1,000 and 40 to 60% by weight of a polyethylene glycol having a weight average molecular weight of 1,000 to 4,000. However, the use of only polyethylene glycol having a weight percentage of less than 1,000 is not preferable because the bio-polyurethane coating fiber produced has poor water resistance.
The polyethylene glycol is preferably 20 to 50% by weight of the total composition. If it is less than 20% by weight, it may be difficult to secure a target moisture permeability. If it is more than 50% by weight, unreacted polyethylene glycol may precipitate after curing. However, as the amount of polyethylene glycol is increased, the moisture permeability is increased. However, excessive addition may cause precipitation or opaque phenomenon, and adhesion and water pressure may be lowered.
(a4) Ethylene glycol
The ethylene glycol serves as a chain extender that induces intermolecular bonding upon formation of the polyurethane by the reaction of the -OH group located at the terminal. Generally, when the amount of the ethylene glycol is increased, the hardness of the polyurethane increases, And a decrease in the number of patients. In the present invention, only ethylene glycol is shown, but a diol chain extender other than the ethylene glycol may be used instead of the ethylene glycol.
Examples of the diol chain extender include diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, May further comprise at least one selected from the group consisting of pentane diol, 1,6-hexane diol, hexylene glycol, neopentyl glycol, 4-cyclohexane dimethanol, trimethylol propane, pentaerythritol, have.
The ethylene glycol may comprise 3 to 5% by weight of 100% by weight of the composition. When added in an amount of less than 3% by weight, water pressure resistance can be satisfied, but the moisture permeability and peel strength are largely deteriorated and the expected physical properties can not be satisfied, and when added in an amount exceeding 5% by weight, water pressure resistance and moisture permeability can not be obtained.
(B) isocyanate
In the present invention, the isocyanate may be an aliphatic or cycloaliphatic group having two or more isocyanate groups (-NCO). The isocyanate may also be fluidically changed according to the desired viscosity.
Examples of the isocyanate include 1,6-hexamethylene diisocyanate, 3,5,5-trimethyl-1-isocyano-3-isocyanatomethylcyclohexane, trimethylhexamethylene diisocyanate, methylene diphenyl diisocyanate, Butene diisocyanate, isophorone diisocyanate, bis (4,4'-isocyanatocyclohexyl) methane, 1,4-cyclohexylene diisocyanate, 4-isocyanate Methyl-1,8-octane diisocyanate and alkyl 2,6-diisocyanatohexanoate having a (C1-C8) alkyl group. The isocyanate may be used singly or in combination of two or more kinds.
In addition to the above-mentioned isocyanates, modified diisocyanates having a functionality of 2 or more and uretdione, isocyanurate, urethane, allophanate, buret, iminooxyadiazin dione or oxadiazinetrione structure, / RTI > ratio. ≪ / RTI >
Preferably, the isocyanate or isocyanate mixture of the above-mentioned type has an isocyanate attached to an aliphatic or cycloaliphatic group, and the functionality of the isocyanate group (-NCO) is 2 or more, preferably 2 to 5.
In the present invention, the isocyanate is preferably contained in an amount of 1 to 200 parts by weight based on 100 parts by weight of the total polyol composition, more preferably 1: 0.8 to 1.2 based on the hydroxyl equivalent number of the polyol composition. When the amount of the polyurethane resin is less than 1 part by weight, the molecular weight of the polyurethane resin is lowered, and the value of the water pressure and the peel strength may be lowered. When the amount exceeds 200 parts by weight, crosslinking of the polyol occurs excessively, it's difficult.
The bio-polyurethane according to the present invention may further contain additives as required. The catalyst of the additive may be selected from the catalysts commonly used in the art, for example, an amine-based catalyst, an organic titanium compound-based catalyst and an organotin compound-based catalyst, and preferably an organotin compound It is preferable to use dibutyl tin dilaurate or di-n-butylbis (dodecylthio) tin as a catalyst.
The chain extender in the additive is a diamine or polyamine such as ethylene diamine, 1,2-diaminopropane, 1, 2-diaminopropane having at least one functional group selected from NH 2 - and NH 3 - components reacting with the isocyanate group of the polyurethane polymer, Diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, isomer mixtures of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methyl Pentamethylenediamine, diethylenetriamine, diaminodicyclohexylmethane and / or dimethylethylenediamine, and the like can be used.
In addition to the primary amino group, a compound having a secondary amino group or an amino group (primary or secondary) as well as an OH group may be used as the chain extender. Examples of these are primary / secondary amines for chain extension or termination such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethyl-aminopropane, 3-amino-1-cyclohexylamino Propane, 3-amino-1-methylaminobutane, alkanolamines such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine and the like.
(Commercially available from Ciba Specialty Chemicals, Ltd.), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) and 2,6-dibutyl-4- Antioxidants such as methyl phenol (BHT); Light stabilizers such as TINUVIN622LD, TINUNIN 765 (manufactured by Ciba Specialty Chemicals), SANOL LS-2626, LS-765 (manufactured by Sankyo Co., Ltd.); Ultraviolet absorbers such as TINUVIN 328 and TINUVIN 234 (manufactured by Chiba Specialty Chemicals Co., Ltd.); Silicone compounds such as dimethylsiloxane polyoxyalkylene copolymer; Addition and reaction type flame retardants such as organic phosphorus compounds and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide and antimony oxide; Pigments such as titanium dioxide, coloring agents such as dyes and carbon black; Hydrolysis inhibitors such as carbodiimide compounds; Fillers such as short glass fibers, carbon fibers, alumina, talc, graphite, melamine and clay; Lubricant; emulsion; Surfactants; Other inorganic extenders; And organic solvents; And the like. It is also possible to add a foaming agent such as water or an alternative flon.
In the polyurethane composition according to the present invention, the fibers can be coated by a method commonly used in the art in the polyurethane composition. For example, plasma coating, nano coating, ink jet, and nano coating as well as direct coating, transfer coating, on-line coating and extrusion coating can be applied, and the present invention is limited thereto It is not.
In the present invention, the fiber to be coated with the polyurethane composition is not limited to natural fibers, synthetic fibers, regenerated fibers, and the like, and is not limited to the fineness and other physical properties of the fibers. It is not limited to fibers, but also to fabrics and nonwoven fabrics.
The polyurethane-coated polyurethane-coated fiber produced by the production method according to the present invention has a water vapor permeability of 5,000 g / m < 2 > / day or more and a water resistance the ㎜ 1,000 and H 2 O can be more than.
Hereinafter, the bio-polyurethane composition according to the present invention and the method for producing the bio-polyurethane-coated fiber prepared therefrom will be described in more detail with reference to Examples and Comparative Examples. However, the following Comparative Examples or Examples are only a reference for explaining the present invention in detail, but the present invention is not limited thereto.
The physical properties of the polyurethane prepared through the following examples and comparative examples were measured as follows.
(Peel strength)
KS K 0533 (Peel Strength Test Method for Adhesive Bags).
(Viscosity)
The Brookfield RV method was applied and the viscosity measured at 150 rpm at 25 ° C and 7th spindle is 30,000 cps.
(Moisture permeability)
The water invert method was used in ASTM E 96 (method for measuring the amount of water vapor permeation of the material). The sample was stored at 23 ° C and 50% RH for 1 hour, and its weight was measured to determine the moisture permeability.
(Water pressure)
It is based on KS K ISO 811 (high pressure hydrostatic pressure method of measuring the water resistance of cloth according to the hydraulic method) and measured using FX 3000 tester (Textest AG).
(IR absorbance)
The IR spectra were confirmed using an FT-IR spectrometer. The permeation rate at 2270 cm -1 was determined by measuring the consumption and reaction progress of -NCO depending on the reaction of the isocyanate group of the hydroxyl group of the polyol and the MDI.
(Bio-polyol)
ASTM D 4252 (chemical analysis method of alcohol ethoxylate and alkylphenol ethoxylate).
(Biomass content)
ASTM D 6866 (Determination of biomass content by radioactive carbon analysis).
(Example 1)
A 500 ml four-necked flask reactor was charged with 32 g of a polyester polyol having a weight average molecular weight of 2,000 Mw and a hydroxyl value of 56 mgKOH / g, and 32 g of a biopolyol having a weight average molecular weight of 2,000 Mw and a hydroxyl value of 55 mgKOH / g. Polyethylene glycol having a weight average molecular weight of 400 ), 4 g of ethylene glycol, and 100 g of dimethylformamide (DMF) were metered in.
Next, a stirrer, a condenser, and a thermometer were installed in the reactor, the temperature was gradually raised to 45 ° C using a mantle, and the mixture was stirred for 30 minutes while maintaining the temperature. Next, heating was stopped, and 44.5 g of methylene diphenyl diisocyanate (MDI) was added and stirred. At this time, the reaction was continued for 2 hours while maintaining the temperature of the reactor at an average temperature of 78 ° C to complete the polyurethane resin.
(Cordura ⓡ 1000D) was coated with Floating knife type (knife thickness: 2 mm), then dried at 130 캜 for 120 seconds, then heated to 150 캜 and dried again for 120 seconds to coat the prepared poly- To complete the coated fiber. The viscosity of the polyurethane resin, the content of the bio polyol, the water pressure of the coated fiber, the moisture permeability and the peel strength were measured and are shown in Table 2.
(Examples 2 to 4 and Comparative Examples 1 to 3)
The procedure of Example 1 was repeated except that the content of the polyurethane composition was changed as shown in Table 1 below. The viscosity of the polyurethane resin, the content of the bio polyol, the water pressure of the coated fiber, the moisture permeability and the peel strength were measured and are shown in Table 2.
[Table 1]
[Table 2]
As shown in Table 1, it can be seen that the bio-polyurethane prepared according to the present invention satisfies all the properties of water pressure, water vapor permeability and peel strength while the content of the bio-polyol is not less than 15% by weight. On the contrary, Comparative Example 1 shows that the water pressure is lowered by using PEG having a smaller molecular weight. In Comparative Example 2 in which the content of ethylene glycol is out of the range of the present invention, the water pressure is satisfied with a reference value of 1000 or more, And in Comparative Example 3, both the water pressure and the water vapor permeability were inferior.
Claims (5)
Wherein the polyethylene glycol is 1 to 99% by weight of a polyethylene glycol having a weight average molecular weight of less than 400 to 1,000 and 1 to 99% by weight of a polyethylene glycol having a weight average molecular weight of 1,000 to 4,000.
Wherein the bio polyol is produced by modifying at least one selected from castor oil, soybean oil, seed oil, woody biomass, and waste glycerol.
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| KR102615530B1 (en) * | 2019-02-28 | 2023-12-19 | 나홍주 | Manufacturing method of dew condensation preventing cloth for air conditioner outlet |
| KR102207612B1 (en) * | 2019-06-18 | 2021-01-26 | 주식회사 비에스지 | Biopolyurethane resin having high-temperature durability, Bio polyurethane film and Manufacturing method thereof |
| KR102306302B1 (en) * | 2019-08-14 | 2021-09-28 | 경기대학교 산학협력단 | Bio polyol and fabricating method of the same |
| KR102409139B1 (en) * | 2020-05-18 | 2022-06-15 | 경기대학교 산학협력단 | Antibacterial bio polyol and fabricating method of the same |
| KR102308231B1 (en) * | 2021-06-11 | 2021-10-01 | (주)코스폴 | Non-toxic two-part type polyurethane adhesive |
| KR102491673B1 (en) * | 2021-06-30 | 2023-01-20 | 이정수 | Manufacturing method of textile fabric with excellent flame retardancy and textile fabric with excellent flame retardancy manufactured thereby |
| KR102491672B1 (en) * | 2021-06-30 | 2023-01-20 | 이정수 | Manufacturing method of eco-friendly fiber fabric with excellent texture and eco-friendly fiber fabric manufactured thereby |
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| KR20140114676A (en) | 2013-03-19 | 2014-09-29 | 한국건설기술연구원 | Nature-friendly Bio-Polyurethane Binder Composition Using Vegetable Oil/Polyol |
| KR101468070B1 (en) | 2013-04-26 | 2014-12-02 | 주식회사 지앤오 코퍼레이션 | Method for manufacturing polyurethane using eco-friendly raw material |
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| JP2003504432A (en) | 1999-07-05 | 2003-02-04 | バイエル アクチェンゲゼルシャフト | Polyurethane dispersion |
| JP2003511486A (en) | 1999-10-02 | 2003-03-25 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | Transesterified polyols for polyurethane prepolymers with adjustable viscosity |
| JP2008208499A (en) | 2007-02-28 | 2008-09-11 | Toray Ind Inc | Sheet-like article and method for producing the same |
| JP2011226047A (en) | 2010-04-02 | 2011-11-10 | Honda Motor Co Ltd | Synthetic imitation leather made by using bio-polyurethane resin |
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