KR101737762B1 - Water-dispersive polyurethane resin for an air-bag and manufacturing process thereof - Google Patents
Water-dispersive polyurethane resin for an air-bag and manufacturing process thereof Download PDFInfo
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- KR101737762B1 KR101737762B1 KR1020150044808A KR20150044808A KR101737762B1 KR 101737762 B1 KR101737762 B1 KR 101737762B1 KR 1020150044808 A KR1020150044808 A KR 1020150044808A KR 20150044808 A KR20150044808 A KR 20150044808A KR 101737762 B1 KR101737762 B1 KR 101737762B1
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
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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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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/93—Applications in textiles, fabrics and yarns
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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
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/30—Environmental or health characteristics, e.g. energy consumption, recycling or safety issues
Abstract
Disclosed is a water-dispersed polyurethane resin for an air bag, which comprises (a) 50 to 70 parts by weight of a hydrophobic polyol, 1.5 to 3.5 parts by weight of a chain extender, 1.5 to 2.5 parts by weight of (hydroxymethyl) propanoic acid (DMPA) and 25 to 35 parts by weight of 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI) 100 parts by weight; (b) 60 to 90 parts by weight of polyethylene glycol having a number average molecular weight of 500 to 1,000 and 40 to 10 parts by weight of 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI) 0 to 40 parts by weight; (c) 1 to 10 parts by weight of at least one amine-based chain extender selected from ethylenediamine and hydrazine, wherein the water-dispersed polyurethane resin is produced by reacting a hydrophobic polyol and 2,2-bis (1-isocyanato-1-methylethyl) benzene (TMXDI) was added and the temperature was raised to 90 占 폚, a dibutyltin dilaurate (DBTDL), heating the mixture to 120 캜, cooling the mixture to 60 캜, and neutralizing triethylamine to prepare an ionic prepolymer; (1-isocyanato-1-methylethyl) benzene (TMXDI) was added and the temperature was raised to 90 占 폚 and dibutyltin dilaurate (DBTDL) was added and the temperature was raised to 120 占 폚 Preparing a nonionic prepolymer by a process; The ionic prepolymer and the nonionic prepolymer prepared as described above are mixed and dispersed in deionized water at 20 to 30 ° C for 10 to 30 minutes through high-speed stirring, and then charged with 1 to 10 parts by weight of an amine chain extender .
Since the water-dispersed polyurethane resin produced by the production method of the present invention is produced without using an organic solvent and a water-soluble solvent (acetone, MEK, NMP) in the manufacturing process, environmental pollution and worker health are not harmed, The ionic prepolymer containing polyol is used singly or mixed with a nonionic prepolymer to disperse the polymer, thereby having excellent dispersibility and sufficient flexibility and toughness when applied to a fiber fabric such as an airbag. The water-dispersed polyurethane resin of the present invention is prepared by mixing an ionic prepolymer and a nonionic prepolymer, dispersing the ionic prepolymer in water, and conducting a chain extension process using a chain extender to produce a water-dispersible polyurethane resin in the form of a block copolymer Dispersible polyurethane resin having a relatively high molecular weight as compared with the conventional water-dispersed polyurethane resin can be synthesized, and it is excellent in air barrier property, hydrolysis resistance, flexural friction, flexibility, etc. Therefore, , Elasticity, resilience, low air permeability, and the like.
Description
The present invention relates to a water-dispersed polyurethane resin for an air bag and a method for producing the same. More specifically, the present invention relates to a process for dispersing and mixing an ionic group- To a water-dispersed polyurethane resin exhibiting sufficient flexibility and toughness when applied to a textile fabric such as an airbag, and a method for producing the same.
Conventional fabric coatings for airbags have problems in environmental regulation by using organic solvents. Accordingly, water-dispersed polyurethane resins are produced by applying a small amount of organic solvent and a water-soluble solvent (acetone, MEK, NMP) Therefore, the manufacturing process of recovering the organic solvent after the production of the resin involves a small amount of the organic solvent and the NMP (high boiling point solvent) in the product, which has the factors that harm the normal environmental pollution of manufacturing and the health of the workers. In particular, in the case of polycarbonate polyurethane, it has been disadvantageous in that it is difficult to produce a solventless type due to an increase in viscosity during the production process.
For this reason, an ionic prepolymer and a nonionic prepolymer having respective advantages in terms of dispersibility and mechanical properties in the preparation of a water-dispersed polyurethane are mixed and dispersed in water and subjected to a chain extension process using a chain extender, Dispersed polyurethane resin having a relatively higher molecular weight than conventional water-dispersed polyurethane resin can be synthesized.
In other words, a conventional process for producing a water-dispersed polyurethane (prepolymer process) involves preparing a prepolymer by mixing a polyol, a dispersant (ionizing agent), a neutralizer, a chain extender of a prepolymer, and an isocyanate and polymerizing the prepolymer at a high temperature , A prepolymer polymerized in high-speed stirring water is added to disperse the prepolymer, and a water-dispersed polymer having an appropriate molecular weight is synthesized through chain extension by adjusting the molecular weight through the polymerization reaction of the dispersed prepolymer through introduction of a chain extender do.
However, in the case of polyether / polyester / polycaprolactam TPU (thermoplastic polyurethane), disadvantages such as chemical resistance, heat resistance, abrasion resistance, rigidity and weather resistance are disadvantageously lowered. However, polycarbonate polyurethane has a chemical resistance, heat resistance, Rigidity, weather resistance, etc. In the case of such a polycarbonate polyurethane, there is a disadvantage that it is difficult to produce a solventless type due to an increase in viscosity during the production process.
That is, the present aqueous dispersion type polycarbonate polyurethane has excellent physical properties, but it has disadvantages in that it is difficult to produce a solvent-free type because its viscosity is easily increased during the manufacturing process as compared with other polyols due to hydrogen bonding characteristics unique to the material. Thus, through the application of TMXDI [1,3-bis (1-isocyanato-1-methylethyl) benzene], it became possible to produce water-dispersible polyurethane resins of relatively low viscosity, A considerable disadvantage has been confirmed in terms of physical properties.
For reference, general water-dispersible polyurethane resins can be largely divided into an ionic resin and a non-ionic resin. Nonionic properties are good in particle stability, but mechanical properties such as mechanical properties, film forming ability, Water-dispersed polyurethane having an ionic functional group is mainly used for maintaining mechanical performance, and water-dispersed polyurethane resin having an ionic functional group has a higher molecular weight, (High molecular weight) water-dispersed polyurethane resin is difficult to synthesize. As a result, the water-dispersible polyurethane resin is used for limited use because it is known that the properties of workability, coatability, stretchability and rebound resilience are lower than that of solvent-type general polyurethane.
The present invention relates to a water-dispersed polyurethane resin for use primarily as a coating fluid for automotive airbag fabrics, the use of airbags has been extended to a number of places other than the front airbag to protect the driver and passengers and the side airbags and inflatable curtains Are now installed in side sections of the vehicle to enhance protection from side impacts or rollovers. This enlarged application of the airbag creates new requirements for the physical characteristics that the airbag exhibits, and it is particularly desirable that the improved air retention performance of the airbag keeps the airbag inflated and maintain its condition for extended periods of time during deployment.
In addition, conventional air bags are generally coated with silicone to increase the weight of the silicone coating by about 0.7 ounces per yard or more, resulting in a bulky and compact product such as a side air bag In addition, it may cause VOC problems in the automobile. Accordingly, the present invention aims at developing a water-dispersed polycarbonate polyurethane resin having an equivalent level or more as compared with an organic solvent-based polyurethane resin, and it has excellent physical properties such as particle safety, coating property, stretchability, rebound resilience and low air permeability And excellent workability.
Prior art for solving the above-mentioned conventional problems is disclosed in Korean Patent Laid-Open No. 2001-0068475, which relates to a method for increasing the molecular weight and adhesion of water-dispersed polyurethane through a chain elongation method, Isocyanate type prepolymer having a carboxyl group terminal is prepared by reacting a polyester polyol containing at least 30% of a crystalline polyol having an average molecular weight of not less than 30, dimethylol propionic acid and an aliphatic isocyanate compound to prepare an isocyanate type prepolymer having a carboxyl group terminal, It is neutralized by adding a sudden amine, then water is added to disperse it and the chain is elongated with a chain extender. When the molecular weight is increased by the chain elongation method as described above, it is possible to obtain an appropriate molecular weight and an adhesive force by merely changing the addition amount of the chain extender. The polyurethane obtained therefrom is an aqueous dispersion type and has excellent safety, It can be used as an adhesive excellent in heat resistance.
In addition, EP 1 426 391 A1 (Belgium, UCB, SA) discloses a hydrophilic NCO-terminated polyurethane prepolymer (PPA) which basically contains no ionic hydrophilic group but contains ionic hydrophilic groups, A hydrophilic NCO-terminated polyurethane prepolymer (PPB) containing nonionic hydrophilic groups obtained by the reaction of a nonionic hydrophilic polyol with a diisocyanate, optionally with a short chain polyol, without a hydrophilic hydrophilic group, However, since the use of only a hydrophilic polyol may cause deterioration of physical properties as compared with a solvent-type polyurethane, there is a possibility that the aqueous polyurethane dispersion obtained from Korean Patent Publication No. 10-2006-0007057 (Dow Corning Corporation, USA) ) Is a reaction product of a silicone component and a polyurethane component Coated fabrics coated with a coating composition comprising a reaction product of a silicone component derived from an aqueous silicone emulsion and a polyurethane component derived from an aqueous polyurethane dispersion provides a fabric coated with the resulting coating agent, . ≪ / RTI > However, the above-described invention shows that when a crosslinked elastomer resin coating is applied to an airbag fabric, it exhibits excellent air retention and gas retention, but is insufficient to improve problems due to weight and volume increase due to the use of silicone resin .
Korean Patent Laid-Open Publication No. 10-2006-0132777 relates to an environmentally friendly water-dispersible PC / PU polyurethane resin having excellent physical and chemical properties. The polyurethane resin does not contain any organic solvent, and as the polyurethane water- A polymer such as a metal catalyst is used as a polymerizable compound having about 40% by weight of solids in the total additive composition and containing no trace amount of a water-soluble solvent or an organic solvent, Discloses an environmentally friendly polyurethane resin which is not used. The polyurethane additive composition according to the present invention may be prepared by adding a polycarbonate diol or a polyether diol and a diol containing a carboxyl group that imparts a hydrophilic group during water dispersion to a diisocyanate compound and stirring the mixture at a temperature of 80-100 ° C , The reaction is carried out at 80-100 ° C for about 2-3 hours, then forcedly dispersed in water, followed by an amine-based long chain extension reaction, and the reaction is terminated by aging the reaction vessel at 30 ° C for 12 hours. .
However, all of the above-described techniques by the known methods can achieve some degree of environmentally friendly functions by being aqueous or water-dispersible. However, the present invention relates to a method for producing an aqueous dispersion of polyurethane, Dispersed polyurethane resin by mixing a hydrophobic prepolymer and optionally a nonionic prepolymer and dispersing it in water and performing a chain extension process using a chain extender to prepare a water-dispersed polyurethane resin in the form of a block copolymer. Dispersed polyurethane resin having a relatively high molecular weight and has completed the present invention.
It is an object of the present invention to provide a process for producing an ionic prepolymer which is excellent in dispersibility by using an ionic prepolymer containing a hydrophobic polyol alone or by mixing it with a nonionic prepolymer without using an organic solvent, Dispersible polyurethane resin for an airbag having sufficient flexibility and toughness when applied to a water-dispersible polyurethane resin, and a process for producing the same.
The water-dispersed polyurethane resin according to the present invention comprises (a) 50 to 70 parts by weight of a hydrophobic polyol, 1.5 to 3.5 parts by weight of a chain extender, 1.5 to 2.5 parts by weight of 2,2-bis (hydroxymethyl) 60 to 100 parts by weight of an ionic prepolymer composed of 25 to 35 parts by weight of 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI) (b) 60 to 90 parts by weight of polyethylene glycol having a number average molecular weight of 500 to 1,000 and 40 to 10 parts by weight of 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI) 0 to 40 parts by weight; (c) 1 to 10 parts by weight of at least one amine-based chain extender selected from ethylenediamine and hydrazine.
According to a preferred embodiment of the present invention, the hydrophobic polyol used in the ionic prepolymer is at least one polyol selected from a polycarbonate polyol (PCD) or polytetramethylene glycol (PTMG) having a number average molecular weight of 1,000 to 3,000, The chain extender used in the ionic prepolymer is characterized by being at least one polyol selected from the group consisting of 1,3 butanediol, 1,4 butanediol, ethylene glycol and trimethylolpropane. The OH / NCO molar ratio of the ionic prepolymer and the nonionic prepolymer is 1.0 to 0.6, and the water-dispersed polyurethane resin has a solid content of 30 to 60% and a viscosity of 7,000 to 12,000 CPS (25 ° C) .
The method for producing the water-dispersed polyurethane resin may further comprise the step of mixing the hydrophobic polyol with 2,2-bis (hydroxymethyl) propanoic acid (DMPA), a chain extender, 1,3-bis (1-isocyanato- Methylethyl) benzene (TMXDI), heating the mixture to 90 DEG C, adding dibutyltin dilaurate (DBTDL) to the mixture, raising the temperature to 120 DEG C, cooling the mixture to 60 DEG C, Preparing an ionic prepolymer; (1-isocyanato-1-methylethyl) benzene (TMXDI) was added and the temperature was raised to 90 占 폚 and dibutyltin dilaurate (DBTDL) was added and the temperature was raised to 120 占 폚 Preparing a nonionic prepolymer by a process; 60 to 100 parts by weight of the ionic prepolymer prepared above and 0 to 40 parts by weight of the nonionic prepolymer were mixed and dispersed in deionized water at 20 to 30 ° C for 10 to 30 minutes through high speed stirring, 1 to 10 parts by weight based on 100 parts by weight of the resin.
The water-dispersed polyurethane resin produced by the production process of the present invention does not harm the environmental pollution and the health of workers because it is produced without using an organic solvent and a water-soluble solvent (acetone, MEK, NMP) , Or by mixing with a nonionic prepolymer to disperse the ionic prepolymer, it has an excellent dispersibility and a sufficient flexibility and toughness when applied to a textile fabric such as an airbag.
The water-dispersed polyurethane resin of the present invention is prepared by mixing an ionic prepolymer and a nonionic prepolymer, dispersing the ionic prepolymer in water, and conducting a chain extension process using a chain extender to prepare a water-dispersible polyurethane resin in the form of a block copolymer Dispersible polyurethane resin having a relatively high molecular weight as compared with the conventional water-dispersed polyurethane resin can be synthesized, and it is excellent in air barrier property, hydrolysis resistance, flexural friction, flexibility, etc. Therefore, , Elasticity, resilience, low air permeability, and the like.
The water-dispersed polyurethane resin according to the present invention comprises (a) 50 to 70 parts by weight of a hydrophobic polyol, 1.5 to 3.5 parts by weight of a chain extender, 1.5 to 2.5 parts by weight of 2,2-bis (hydroxymethyl) propanoic acid (DMPA) 60 to 100 parts by weight of an ionic prepolymer composed of 25 to 35 parts by weight of 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI) (b) 60 to 90 parts by weight of a polyethylene glycol having a weight average molecular weight of 500 to 1,000 and 40 to 10 parts by weight of 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI) 0 to 40 parts by weight; (c) 1 to 10 parts by weight of at least one amine-based chain extender selected from ethylenediamine and hydrazine.
Hereinafter, a method for producing the water-dispersed polyurethane resin according to the present invention will be described, but it is to be understood that those skilled in the art will readily appreciate that the present invention can be easily carried out by those skilled in the art. It is not intended to limit the technical spirit and scope of the present invention.
First, the step of preparing an ionic prepolymer comprises reacting a hydrophobic polyol with 2,2-bis (hydroxymethyl) propanoic acid, a chain extender, 1,3-bis (1-isocyanato- And heating the mixture to 90 ° C., adding dibutyltin dilaurate (DBTDL), raising the temperature to 120 ° C., cooling the mixture to 60 ° C., adding triethylamine and neutralizing the mixture, and separately preparing a nonionic prepolymer (1-isocyanato-1-methylethyl) benzene, and heating the mixture to 90 DEG C and adding dibutyltin dilaurate (DBTDL) to raise the temperature to 120 DEG C Process.
The hydrophobic polyol used in the ionic prepolymer is preferably at least one polyol selected from a polycarbonate polyol (PCD) or a polytetramethylene glycol (PTMG) having a number average molecular weight of 1,000 to 3,000, Although there is no particular limitation on the specific kind of the extender, in the present invention, as a result of repeatedly repeated experiments, it has been found that the extender can be at least one selected from the group consisting of 1,3 butanediol, 1,4-butanediol, ethylene glycol and trimethylolpropane It has been found desirable to use polyols.
As a result, the OH / NCO molar ratio of the ionic prepolymer and the nonionic prepolymer is 1.0 to 0.6. The polyol is reacted with isocyanate to produce a polyurethane (PU) Active hydrogen compounds having two or more active hydrogen groups such as a hydroxyl group, a carboxyl group and an amine group in the molecule, and the use of these polyols is classified depending on the molecular weight thereof. Examples of the active hydrogen compounds include ethylene glycol, glycerine, Butanediol, trimethylol propane and the like and low molecular weight polyols are used as chain extenders or crosslinking agents, and high molecular weight polyols having an average molecular weight of up to 8,000 are used for the production of actual PU. The structure of the polyol greatly influences the properties of the final PU product. Particularly in the case of the polyether polyol, the starting material used in the production, the kind of the epoxide and the molecular weight of the polyol chain, Type, content, ratio, and distribution state of the product.
Therefore, various kinds of polyols are used depending on molecular structure, molecular weight, functionality and OH-value, and have a direct influence on the physical properties of PU. Polyester polyols, for example, are preferred due to the high strength of the ester structure, and the results of studying the physical properties of the foam produced using the polyester polyol have been reported. The polyol is excellent as the functional group is large, the viscosity is low, and the price is low, and studies for synthesizing such a polyol have been progressing in various aspects in recent years.
Finally, the step of introducing the amine chain extender is carried out by mixing the ionic prepolymer and the nonionic prepolymer prepared as described above, dispersing the mixture in deionized water at 20 to 30 ° C for 10 to 30 minutes through high-speed stirring, The chain extender is introduced. The use of at least one selected from the group consisting of ethylenediamine and hydrazine is preferable because the urethane resin can be polymerized in a high viscosity and high molecular weight, Dispersible polyurethane having good dispersibility can be produced by mixing a nonionic polyurethane prepolymer and an ionic prepolymer which do not use ion exchangers such as DMPA and an ionic prepolymer at a certain ratio, The reaction is carried out.
At this time, the ionic prepolymer acts as an emulsifier to emulsify a non-ionic prepolymer containing no ion-introducing agent into water. Therefore, the amount of the ion-introducing unit (DMPA) It is possible to prepare a water-dispersed polyurethane which can complement the dispersion stability and the mechanical property deterioration which is a disadvantage of the non-ionic prepolymer, which is a disadvantage of the styrene-based prepolymer. Moreover, It is possible to produce a polyurethane resin.
The water-dispersed polyurethane resin prepared as described above has a solid content of 30 to 60% and a viscosity of 7,000 to 12,000 CPS (based on 25 ° C). The polyurethane resin having a high viscosity and a high molecular weight generally has a coating property, , Repulsive elasticity, and the like, it is possible to prepare a water-dispersible polyurethane resin having a comparatively high viscosity. Accordingly, the viscosity of the resin is adjusted by using a thickener or water to adjust the process conditions in the conventional fiber coating process Can be minimized, thereby further improving the workability.
Hereinafter, the present invention will be described by way of examples in which the water-dispersed polyurethane resin is experimentally tested. Hereinafter, the present invention will be described with reference to preferred embodiments which are easily understood and practiced by those skilled in the art.
- Synthesis of prepolymer
Ionic prepolymer A: In a four-necked 1 L reactor, polycarbonate diol 1000 (PCDL1000 / 250 g), 1,3 butadiene (1,3BD / 6.55 g), 2,2- bis (hydroxymethyl) propanoic acid (DMPA / (1-isocyanato-1-methylethyl) benzene (TMXDI / 97.72 g), and the mixture was stirred to uniformly mix at 90 占 폚. Then, dibutyltin dilaurate (DBTDL) was added and reacted at 120 ° C. for 3 to 4 hours. After cooling to 60 ° C., triethylamine (TEA / 3.66) was added.
Nonionic prepolymer B: Polyethylene glycol 600 (PEG 600/150 g) and 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI / 74 g) were placed in a four- And stirred to be mixed. Then, dibutyltin dilaurate (DBTDL) was added and reacted at 120 ° C for 3 to 4 hours, followed by cooling to 60 ° C.
- dispersion and chain extension
Prepolymer A and prepolymer B prepared as described above are mixed and slowly added to 1,300 g (25 ° C) of the previously prepared deionized water. At this time, the temperature should not exceed 30 ° C and the time should be within 30 minutes. Dilute 2.5 g of ethylenediamine in 65 g of deionized water. As a result, a water-dispersed polycarbonate polyurethane resin having a solid content of 30% and a viscosity of 10,000 CPS / 25 占 폚 was obtained.
- Synthesis of prepolymer
(PCDL1000 / 350g), 1,4-butanediol (1,4BD / 8.06g), 2,2-bis (hydroxymethyl) propanoic acid (DMPA / 5.1g), and 1 , And 3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI / 97.72 g) were added and stirred to be uniformly mixed at 90 ° C. Then, dibutyltin dilaurate (DBTDL) was added and reacted at 120 ° C for 3 to 4 hours, followed by cooling to 60 ° C.
- dispersion and chain extension
Triethylamine (TEA / 3.66 g) was added to 1,000 g of deionized water, cooled to 25 캜, and the prepared prepolymer was added slowly. At this time, the temperature should not exceed 30 ° C and the time should be within 30 minutes. Then 1.4 g of hydrazine is diluted to 80 g of deionized water. As a result, a water-dispersed polycarbonate polyurethane resin having a solid content of 30% and a viscosity of 8,000 CPS / 25 캜 was obtained.
- Synthesis of prepolymer
(PCDL2000 / 200g), polytetramethylene glycol (PTMG2000 / 100g) 1,3-butanediol (1,3BD / 0.07g), 2,2-bis (hydroxymethyl) propane (DMPA / 11.94 g) and 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI / 94.69 g) were added and stirred at 90 ° C to be uniformly mixed. Then, dibutyltin dilaurate (DBTDL) was added and reacted at 120 ° C for 3 to 4 hours, followed by cooling to 60 ° C.
- dispersion and chain extension
Triethylamine (TEA / 8.57 g) was added to 254.2 g of deionized water, cooled to 25 占 폚, and the prepared prepolymer was added slowly. The temperature should not exceed 30 ℃ and the time should be within 30 minutes. Then, 0.16 g of ethylenediamine was diluted in 3 g of deionized water and added. As a result, a water-dispersed polycarbonate polyurethane resin having a solid content of 35% and a viscosity of 12,000 CPS / 25 캜 was obtained.
[Experimental Example]
Table 1 below shows the results of measuring the performance of the coating experiment using the water-dispersed polycarbonate polyurethane resin prepared according to Examples 1 to 3 and the general organic solvent-type polycarbonate polyurethane resin as a comparative example.
It can be seen from the results of Table 1 that the water-dispersed polyurethane resin of the present invention can be obtained by mixing an ionic prepolymer containing a hydrophobic polyol with a nonionic prepolymer alone or in combination with a nonionic prepolymer to obtain a polymer having a tensile strength, elongation, edge comb resistance, Air permeability, and flexural strength, it meets the quality standard value of the coating product for airbag, and it is confirmed that it shows superior physical characteristics compared with the comparative example using general organic solvent type polyurethane resin .
Accordingly, the water-dispersed polyurethane resin produced according to the present invention can be variously substituted, modified and changed without departing from the technical idea of the present invention. The water-dispersed polyurethane resin can be used for various airbag materials as well as dispersion stability, , Rebound resilience, low air permeability, and the like can be used in various applications and forms as functional materials for various textile products.
Claims (8)
(1-isocyanato-1-methylethyl) benzene (TMXDI) was added and the temperature was raised to 90 占 폚 and dibutyltin dilaurate (DBTDL) was added and the temperature was raised to 120 占 폚 Preparing a nonionic prepolymer by a process;
Mixing the ionic prepolymer and the nonionic prepolymer prepared as described above, dispersing the mixture in deionized water at 20 to 30 ° C for 10 to 30 minutes through high-speed stirring, and then introducing an amine chain extender;
By weight based on the total weight of the polyurethane resin.
Wherein the hydrophobic polyol used for preparing the ionic prepolymer is at least one polyol selected from polycarbonate polyol (PCD) or polytetramethylene glycol (PTMG), and has a number average molecular weight of 1,000 to 3,000. A method for producing a resin.
Wherein the hydrophilic polyol used for preparing the nonionic prepolymer is a polyethylene glycol (PEG) having a number average molecular weight of 500 to 1,000.
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| KR101939978B1 (en) * | 2017-03-29 | 2019-01-18 | 주식회사 빅스 | Hydrophilic water-dispersive polyurethane resin for textile skin coating and manufacturing process of a hydrophilic film used it |
| CN114106288B (en) * | 2021-11-04 | 2022-12-06 | 江南大学 | Preparation method and application of waterborne polyurethane dispersant |
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| KR100341870B1 (en) | 2000-01-06 | 2002-06-24 | 김중현 | Process for preparing aqueous polyurethane |
| EP1426391A1 (en) | 2002-12-07 | 2004-06-09 | Ucb, S.A. | Aqueous polyurethane dispersions and their use for preparation of coatings that are permeable to water vapor |
| US20060217016A1 (en) | 2003-06-04 | 2006-09-28 | Shaow Lin | Silicone/polyurethane coated fabrics |
| KR100812635B1 (en) | 2006-12-04 | 2008-03-13 | 현대하이켐(주) | Dispersion polycarbonate polyurethane resin |
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| JP2007092195A (en) | 2005-09-27 | 2007-04-12 | Dai Ichi Kogyo Seiyaku Co Ltd | Aqueous resin composition for fiber laminate skin, method for producing fiber laminate, and synthetic leather |
| KR100793259B1 (en) | 2006-12-29 | 2008-01-10 | (주)디피아이 홀딩스 | Waterborne polyurethane resin, method of manufacturing the waterborne polyurethane and method of dispersing carbon nano tube using the waterborne polyurethane |
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