KR101744487B1 - Polyurethane resin compositions for a non-swelling permeable waterproof cloth used surface activated nano-silica particles - Google Patents
Polyurethane resin compositions for a non-swelling permeable waterproof cloth used surface activated nano-silica particles Download PDFInfo
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- KR101744487B1 KR101744487B1 KR1020150158570A KR20150158570A KR101744487B1 KR 101744487 B1 KR101744487 B1 KR 101744487B1 KR 1020150158570 A KR1020150158570 A KR 1020150158570A KR 20150158570 A KR20150158570 A KR 20150158570A KR 101744487 B1 KR101744487 B1 KR 101744487B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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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- 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
The present invention relates to a polyurethane resin composition for a non-swellable moisture-permeable and waterproofing membrane using surface-treated nanosilica particles, and more particularly, to a polyurethane resin composition for surface-treated nanosilica particles, which comprises a hydrophobic polyurethane resin and a silane compound having a particle size of 10 to 1,000 nm 10 to 15 parts by weight of silicate coupled with a polyethylene glycol macromer is uniformly mixed.
The polyurethane resin composition for a non-swellable moisture-permeable and waterproofing sheet using the surface-treated nanosilica particles of the present invention comprises a silane compound and a polyethylene glycol macromer on the surface of the nanosilica particles added to the hydrophobic polyurethane resin, Is highly compatible with the polyurethane resin and the solvent and is excellent in the moisture permeability without causing swelling due to moisture permeation.
Further, the moisture-permeable and water repellent foam formed by the polyurethane resin composition of the present invention in the form of a film having a thickness of about 10 to 30 탆 has a remarkably reduced swelling phenomenon in the appearance of moisture permeability and has a good aesthetic appearance, Hydrophobicity, so that the hydrolysis resistance against moisture is excellent, and the durability is improved.
Description
The present invention relates to a polyurethane resin composition for surface-treated nanosilica particles, and more particularly to a polyurethane resin composition for a non-swellable moisture-permeable and waterproofing polyurethane resin, which comprises a silane compound and a polyethylene glycol Polyethylene glycol macromer contains silicate which is coupled with polyurethane resin and solvent so that it has hydrophilic property while having high density of material. Therefore, it is made into a moisture permeable film of film type Non-swellable moisture-permeable waterproofing using surface-treated nanosilica particles that can impart excellent durability, aesthetic appearance, and good moisture permeability due to excellent hydrolysis resistance to moisture and swelling caused by moisture penetration Containing polyurethane resin composition.
The moisture permeable waterproof material has been developed before the process of the porous film coating method, and since the middle of the 1960s, a microporous coating of water-absorbing micropores The product was developed. This product was excellent in moisture permeability but it could not be fixed due to pinhole leakage, hardening of the feeling due to cold, and heavy feeling of the product. In developed countries, since the mid-1970s, the sports boom has started and demand for breathable and waterproof has been strongly demanded. At this time, moisture permeation defoamer by porous film coating method has strongly impacted all manufacturers including academia and industry at that time .
As described above, the waterproofing product has already been developed, but the problem of stickiness due to condensation can not be solved, and how to impart moisture permeability has been a major problem at the time. The basic principle of the moisture permeable and waterproofing material forming the microporous membrane Has been proposed by coatings, and research and development has become active in the industry. As a result, a coating product having a porous film was developed, in which a wet coating of polyurethane was developed, and a microporous coating of a dry acrylic resin was developed from 1980, and thereafter a urethane, acrylic and wet, Microporous machining technology has also appeared.
Goretex (first generation) sold in 1977 pointed out problems such as oil contamination due to oil retention and deterioration of water resistance due to surfactants. In 1979, a modified fluorine film was used to apply a thin layer of resin Waterproof material (2nd generation) was also developed. For these post-processing products, high-density fabrics made of split-type composite fibers in 1981 and high-density polyester fabrics made of microfibers in 1983, non-coating moisture-proof fabrics, were also developed. These high-density fabrics compete with post-processing products in some parts and establish a field of breathable and waterproof material, which is prepared with high-density fabric in post-processing and emotion.
In the first half of 1980s, improvement of basic functions such as water pressure, moisture permeability, warmth, stretch and other new functions have been progressed. The functional surface has been dewatered to prevent condensation, and high moisture permeability and moisture absorption and deodorization imparted by using natural polymer materials have been advanced, and a heat storage type that absorbs sunlight has been developed even in warmth. In the 1990s, the decline in unit price was the main factor, and consumers were avoided because they used the appropriate level for the purpose of use and excessively excessive function was a factor that raised the unit price. Accordingly, the basic performance of functional materials such as improvement of water pressure while maintaining high moisture permeability up to the present, low water pressure due to washing, no rustling sound, high peeling strength, and improvement of touch by polar membrane The main theme is to improve wearing comfort.
At present, the most important class in the development of moisture permeable and waterproof materials is the improvement of the water pressure. The improvement of the water pressure should be developed in the direction of increasing the water pressure while maintaining the balance with the moisture permeability and maintaining the moisture permeability. In fact, it is difficult to improve both functions at the same time. Based on a high water pressure resistance is in the target substantially 5,000mmH 2 O or more, when the water pressure must be limited to only this method than the lamination coating and high performance, the 20,000mmH 2 O level, water pressure resistance of at least 10,000mmH 2 O When the imperforate film quality Can be obtained. The coating is estimated to be compared with the water pressure laminate is from about 2 O 5,000mmH relatively low degree 10,000mmH 2 O, it is high up to 20,000mmH 2 O, but does not prevent to use for clothing in about 2,000mmH 2 O .
Although there is no prescribed regulation for moisture permeability, it is often required to have a high humidity of 4,000g / ㎡24hrs or more. Nowadays, a product improved to 8,000g / ㎡24hrs is being developed. In order to improve the moisture permeability, it is often used to make the coating layer thinner to increase the porosity of the coating, which in turn decreases the water pressure. For this reason, researches are being conducted such as coating a multilayer structure with a hydrophilic resin and using a natural polymer material. In addition, a selective evaporation method using a W / O type emulsion also provides a thin film having a high moisture permeability. In order to increase the moisture permeability, it is necessary to increase the condensation suppression effect, and it is impossible to completely prevent condensation from occurring. Generally, it can be said that the water vapor permeability of the clothes is more than 3,000 g / cm 2 24 hrs. However, when the outside temperature is high, a large amount of perspiration may be followed temporarily.
As described above, in the case of the moisture permeable and waterproof material for clothes, since the functions such as water pressure and moisture permeability are most important, all research and development are concentrated on high functionality, but in order to improve the moisture permeability, the film thickness is decreased to decrease the porosity Increased products adversely affect water pressure. In addition, when an excessively hydrophilic material is introduced to increase the moisture permeability, the waterproofing and moisture permeability is excellent when used for actual clothing, but when exposed to water such as snow, rain or sweat for a long time, the hydrophilic film layer swells, And thus the appearance is greatly damaged. When the water repellency of the clothes is deteriorated due to washing of the moisture permeable and waterproof clothing, such a phenomenon occurs more severely. When the film layer is swollen, all the strength and physical properties are weakened. There is a problem that the functionality is greatly deteriorated.
In order to solve such a problem, Korean Patent Registration No. 10-0909677 discloses a hydrophilic polyurethane composition comprising at least one surface of a moisture permeable waterproof film and a moisture permeable waterproof film, wherein the hydrophilic polyurethane composition is composed of at least three solvents different in boiling point from the hydrophilic polyurethane resin Swellable film comprising a monolithic membrane formed by subjecting a solvent contained in the hydrophilic polyurethane composition to a heat treatment at a boiling point temperature and a solvent having a boiling point higher than that of the solvent having the lowest boiling point, However, there is a difficulty in the process of manufacturing a monolithic membrane by performing a multi-stage heat treatment on the laminated film.
Korean Patent Laid-Open Publication No. 10-2014-0082161 discloses a hydrophilic polyurethane film which is excellent in moisture permeability, water pressure, smooth touch, excellent in peel strength and durability, In order to solve the problem caused by the swelling of the film layer and to impart high moisture permeability, a nano-state fine particulate component having excellent hygroscopicity is introduced, and an additive capable of forming nano- The present invention relates to a highly functional laminating moisture-proofing protective film and a method of manufacturing the same. In the method of manufacturing the highly functional laminating moisture-proofing protective film, a resin composition comprising a highly hydrophobic resin, nano- To form a microporous film layer; And a step of laminating the film layer by bonding the entire surface of the film layer with a polyurethane adhesive or by bonding the layer with the fabric.
In addition, in the nanosilica-containing polycyanate ester composition described in Korean Patent Laid-Open Publication No. 10-2014-0090259 (Applicant: 3M Innovative Properties Company, USA), the curable polycyanate ester resin and There is provided a curable resin sol having a colloidal dispersion of substantially spherical surface-modified silica nanoparticles, wherein the curable resin sol is a mixture of silica nanoparticles and a hardenable poly cyanate ester Based on the total weight of the resin, of up to 200 weight percent of alkali and alkaline earth metal ions. Compositions comprising such curable resin sols and reinforcing fibers, processes for making such compositions, and various articles made using such curable resin sols and compositions are also provided.
On the other hand, in the present invention, rather than imparting moisture permeability to a polyurethane resin having moisture permeability to a urethane resin, a silane compound and a silicate coupling with a polyethylene glycol micro- The present invention has been completed by developing a polyurethane resin composition for breathable waterproofing which can impart moisture permeability.
It is an object of the present invention to provide a hydrophobic polyurethane resin composition which contains a silicate compound and a polyethylene glycol macromer-linked silicate on the surface of a nanosilica particle added to a hydrophobic polyurethane resin, When the film is formed into a moisture-permeable tarpaulin in the form of a film because it has good compatibility with a solvent and has a high density of material and is hydrophobic, swellability due to moisture penetration is excellent due to excellent hydrolysis resistance against moisture Swellable waterproof breathable polyurethane resin composition using surface-treated nanosilica particles which can provide excellent durability, aesthetic appearance, and good moisture permeability.
The polyurethane resin composition for a non-swellable moisture-permeable and waterproofing sheet using the surface-treated nanosilica particles according to the present invention comprises a silane compound on the surface of a nanosilica having a particle size of 10 to 1,000 nm based on 100 parts by weight of a hydrophobic polyurethane resin. And 10-15 parts by weight of silicate coupled with a polyethylene glycol macromer are uniformly mixed with each other.
According to a preferred embodiment of the present invention, the silane compound may include 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxy propyl trimethoxysilane, and the polyethylene glycol macromer is any one selected from the group consisting of a number average molecular weight of 950, 1500 and 4,000. Poly (ethylene glycol) methyl ether methacrylate (poly (ethylene glycol) methyl ether methacrylate} is used.
The polyurethane resin composition may further comprise 5 to 15 parts by weight of dimethylformamide (DMF) relative to 100 parts by weight of the hydrophobic polyurethane resin; 15 to 25 parts by weight of toluene (Toluene); And 15 to 25 parts by weight of methylethylketone (MEK), so that the viscosity is about 3,000 to 3,200 cps (25 캜).
And by coating the polyurethane resin composition on a release liner may be formed from a breathable tarpaulin of a film thickness of 10 ~ 30㎛ form, and moisture-permeable film of the tarpaulin type water pressure 10,000mmH 2 0 (ISO 0811) or more, the moisture permeability 7700 g / m < 2 > 24hrs (JIS L 1099A-1 method).
The polyurethane resin composition for a non-swellable moisture-permeable and waterproofing sheet using the surface-treated nanosilica particles of the present invention comprises a silane compound and a polyethylene glycol macromer on the surface of the nanosilica particles added to the hydrophobic polyurethane resin, Is highly compatible with the polyurethane resin and the solvent and is excellent in the moisture permeability without causing swelling due to moisture permeation.
Further, the moisture-permeable and water repellent foam formed by the polyurethane resin composition of the present invention in the form of a film having a thickness of about 10 to 30 탆 has a remarkably reduced swelling phenomenon in the appearance of moisture permeability and has a good aesthetic appearance, Hydrophobicity, so that the hydrolysis resistance against moisture is excellent, and the durability is improved.
Hereinafter, a method for preparing a polyurethane resin composition for a non-swellable moisture-permeable and waterproofing membrane using the surface-treated nanosilica particles according to the present invention will be described in detail. So as not to imply that the technical idea and scope of the present invention are limited.
Generally, a polyurethane resin is a resin produced on the basis of a urethane bond formed by the reaction of an isocyanate group (-NCO) with a hydroxyl group (-OH) in a polymer, and a polyol, isocyanate, Various solvents are added to prepare a solution polymerization method. The characteristics of the polyurethane resin are that it is possible to produce a thin coating film because of its large film strength and high adhesive strength, and it is possible to produce a porous film film by softening the feel by abundant elasticity of the coating film and providing moisture permeability and breathability, And since it is processed without using a plasticizer, there is little workability problem caused by the plasticizer.
The polyurethane resin can be divided into a hydrophilic type and a hydrophobic type according to raw materials used. The hydrophilic polyurethane resin is made of polyethylene glycol (PEG) as a raw material, Can be synthesized. However, in the case of hydrophilic polyurethane using PEG, swelling occurs, which is not good for cosmetics, and is easily degraded to water or sweat because of poor hydrolysis resistance. On the other hand, the hydrophobic polyurethane resin can be manufactured by using a polytetramethylene ether glycol (PTMG), a polypropylene glycol (PPG), a polyester polyol, a polycarbonate polyol, This hydrophobic resin can be produced. The hydrophobic urethane resin is excellent in durability without mixing with water, and has high water resistance and oil resistance when fully cured.
According to the prior art, in order to impart high moisture permeability to a fabric in a manufacturing method of a laminating moisture-proofing and defoaming agent, a nano-state fine particle component having excellent hygroscopicity such as silica or silicate is added to a polyurethane adhesive in an amount of 5 to 30 wt. It is known that nano-sized fine pores can be formed by injecting a large amount of fine particles having a porosity and an absorbency in order to improve the moisture permeability. However, due to poor dispersibility of particles and weakness of the film, Which can cause serious side effects.
In order to develop moisture permeability, the polyurethane material for functional breathable waterproofing which is currently on the market is mostly produced by using a polyol such as polyethylene glycol as a raw material. This raw material plays a role of expressing the moisture permeability, Hydrolysis) or sweat, swelling occurs and the durability is not good. In the case of a material which does not cause swelling, the application is often difficult and expensive.
In order to solve this problem, in the present invention, the polyurethane glycol having moisture permeability is bonded to the urethane resin to impart moisture permeability, and a silane compound and a polyethylene glycol micromer-linked silicate are mixed on the surface of the nanosilica particles as an additive to reduce swelling Waterproofing polyurethane resin composition capable of imparting moisture permeability as well as moisture permeability to water.
The present invention relates to a process for producing a polyurethane resin composition, which comprises using a urethane resin to silane compound (s) on the surface of a nanosilica having a particle size of 10 to 1,000 nm and 100 g / m < 2 > of a hydrophobic polyurethane resin in order to exhibit moisture permeability while remarkably reducing swelling, And 10-15 parts by weight of silicate (Polyethylene glycol macromer) -coupled silicate is uniformly mixed.
That is, the surface treatment of the nanosilica particles is a step of coupling the silane compound to the nanosilica and adding the polyethylene glycol macromer capable of imparting the moisture permeability to the nanosilica particle. The nanosilica surface treatment is performed with a silicate combined with a silane compound and a polyethylene glycol macromer The swelling phenomenon of the polyurethane resin can be remarkably reduced and the moisture permeability can be exhibited.
In the case of the silane compound, a silane coupling agent having a double bond may be used. Examples of the silane coupling agent include 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl methyl The surface of the nanosilica is treated with at least one material selected from among dimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and 3-acryloxypropyl trimethoxysilane, The hydrophilicity of the nanosilica is blocked completely or the nanosilica surface has strong hydrophobicity, the moisture permeability may not be satisfactory. Therefore, the most suitable type of silane compound is selected.
The chemical structure of the silica particles and the 3-methacryloxypropyltriethoxysilane is shown in the following Reaction Scheme 1.
<Reaction Scheme 1>
After the reaction, if a polyethylene glycol macromer is added for the moisture-permeable development and the radical reaction proceeds, the surface treated nanosilica having the chemical structure as shown in the following reaction formula 2 can be obtained.
<Reaction Scheme 2>
The polyethylene glycol macromer may be any one selected from the group consisting of poly (ethylene glycol) methyl ether methacrylate having a number average molecular weight of 950, 1500 and 4,000 And it is analyzed that the reactivity with the silane compound is lowered when the molecular weight of the polyethylene glycol macromer is out of the above range. In general, macromers are polymers with high reactivity designed to introduce functional groups as terminal reactive macromolecules that are polymers with polymerizable groups at the ends of the polymer chains.
Also, in the present invention, toluene is used as a solvent for the uniformity and convenience of the reaction in the surface treatment of the nanosilica, and it is preferable to adjust the ratio of the nanosilica and toluene to a weight ratio of 1/5 to 1/20. After the completion of the reaction, the solvent and the unreacted silane can be removed by filtration under reduced pressure. After the filtration under reduced pressure, the obtained silicate is washed 5 times (3 to 7 times) with ethanol, 110 ° C) in a dry oven for about 10 hours (5 to 15 hours) can stably form a silicate compound suitably coupled to the surface of the nanosilica with a silane compound and a polyethylene glycol macromer.
The polyurethane resin composition according to the present invention is a nano-state absorbent microparticle obtained by surface-treating nano silica having a particle size of 10 to 1,000 nm with a silane compound and a polyethylene glycol macromer, and then adding 100 parts by weight of the hydrophobic polyurethane resin The nano-state silicate has a good specific surface area, so that the moisture permeation protection fabric made of the polyurethane resin composition is remarkably reduced in swelling with respect to moisture, Function.
If the silicate is contained in an amount of less than 10 parts by weight, the swelling phenomenon and the water pressure are excellent but the moisture permeability is poor. If the silicate is more than 15 parts by weight, the swelling phenomenon and the moisture permeability are excellent, but the water pressure may be poor. The viscosity of the polyurethane resin composition is preferably about 3,000 to 3,200 cps (based on 25 ° C), considering that the mixing and dispersing properties of the silicate incorporated in the polyurethane resin are very important factors for the quality of the product.
Since the nano-state silicate has a particle size of 10 to 1,000 nm, the polyurethane resin composition containing the nano-state silicate has good compatibility with the polyurethane resin and the solvent unlike the conventional nanosilica. Therefore, the polyurethane resin composition containing the silicate has a low density, hydrophobic), and when it is manufactured as a moisture permeable waterproof film of film type, not only water resistance and oil resistance but also durability are excellent, and swelling due to moisture penetration hardly occurs.
The polyurethane resin composition can be coated by including a solvent. The solvent is not particularly limited as long as it is compatible with the polyurethane resin. In the present invention, 100 parts by weight of the hydrophobic polyurethane resin And 10 to 15 parts by weight of silicate, when the solvent is mixed in the range of 35 to 65 parts by weight, a film having a high viscosity of about 3,000 to 3,200 cps (based on 25 ° C) and excellent moisture permeability is formed It has been studied not only that it is suitable but also that the durability of the product is excellent.
In particular, the solvent used in the present invention is a complex solvent comprising 5 to 15 parts by weight of dimethylformamide (DMF), 15 to 25 parts by weight of toluene (toluene) and 15 to 25 parts by weight of methylethylketone (MEK) It is possible to maximize the solubility in the polyurethane resin, so that the durability and the airtightness of the coating film are maintained for a long time.
Also, the polyurethane resin composition may be coated on a release paper to form a moisture-permeable waterproofing film having a thickness of 10 to 30 占 퐉. The moisture permeable waterproofing foam formed in the film form has a thin thickness, It can be used for high-performance products with a water pressure of about 10,000 mmH 2 0 (ISO 0811) and a moisture permeability of about 8,000 g / ㎡ 24 hrs (JIS L 1099A-1 method).
However, in the case of the functional product which is conventionally permeable to moisture, the pore type has a disadvantage in that the film strength is low and the process is difficult, and the non-porous type is hydrophilic and poor in hydrolysis resistance and swell, The waterproofing fabric according to the present invention is easy to manufacture and does not cause swelling even when it is exposed to water for a long period of time, and has high strength and hydrolysis resistance of the film.
Hereinafter, a polyurethane resin composition for a non-swellable moisture-permeable and waterproofing sheet using the surface-treated nanosilica particles according to the present invention will be described. However, it should be understood that the present invention is not limited to the specific examples The present invention will be described.
[Example 1]
100 g of nano silica and 1 L of toluene are put into a 2-liter three-neck reflux reactor and stirred well. Then, 62.08 g of 3-methacryloxypropyl triethoxysilane was added, and the temperature was slowly raised, and the reaction was carried out at 60 ° C for 4 hours. After the temperature of the reactor was lowered to 40 ° C or less, 237 g of poly (ethylene glycol) methyl ether methacrylate (molecular weight: 950) was slowly added dropwise to the reaction system (about 3 hours).
The reaction product is filtered through reduced pressure to remove toluene, and then washed five times with ethanol. Thereafter, the resultant was dried in a dry oven at about 100 ° C. for 24 hours to synthesize a silicate in which a silane compound and a polyethylene glycol macromer were coupled to the nanosilica as a final material.
[Example 2]
100 g of nano silica and 1 L of toluene are put into a 2-liter three-neck reflux reactor and stirred well. Then, 62.08 g of 3-methacryloxypropyl triethoxysilane was added thereto, and the mixture was slowly heated and reacted at 60 ° C for 4 hours. After the reactor temperature is lowered to 40 ° C or less, 375 g of poly (ethylene glycol) methyl ether methacrylate (molecular weight: 1500) is slowly added dropwise (about 3 hours).
The reaction product is filtered through reduced pressure to remove toluene, and then washed five times with ethanol. Thereafter, the resultant was dried in a dry oven at about 100 ° C. for 24 hours to synthesize a silicate in which a silane compound and a polyethylene glycol macromer were coupled to the nanosilica as a final material.
[Example 3]
15 parts by weight of the silicate synthesized in Example 1, 10 parts by weight of DMF, 20 parts by weight of Toluene and 20 parts by weight of MEK were added to 100 parts by weight of the hydrophobic polyurethane resin and dispersed for 15 minutes using a homomixer to prepare a coating solution Viscosity 3,000 to 3,200 cps at 25 ° C). The prepared coating solution was formed into a film having a thickness of 20 μm with a comma knife on a release paper and dried at about 120 ° C. for 1 minute and 30 seconds to prepare a film.
[Example 4]
15 parts by weight of the silicate synthesized in Example 2, 10 parts by weight of DMF, 20 parts by weight of Toluene and 20 parts by weight of MEK were added to 100 parts by weight of the hydrophobic polyurethane resin and dispersed for 15 minutes using a homomixer to prepare a coating solution Viscosity 3,000 to 3,200 cps at 25 ° C). The prepared coating solution was formed into a film having a thickness of 20 μm with a comma knife on a release paper and dried at about 120 ° C. for 1 minute and 30 seconds to prepare a film.
[Comparative Example 1]
100 g of nano silica and 1 L of toluene are put into a 2-liter three-neck reflux reactor and stirred well. Then, 62.08 g of 3-methacryloxypropyl triethoxysilane was added thereto, and the mixture was slowly heated and reacted at 60 ° C for 4 hours. Thereafter, the reaction product is subjected to filtration under reduced pressure to remove toluene and then washed five times with ethanol. Then, it was dried in a 100 ° C dry oven for 24 hours to synthesize a silicate in which a silane compound was coupled to nano silica.
[Comparative Example 2]
15 parts by weight of the silicate synthesized in Comparative Example 1, 10 parts by weight of DMF, 20 parts by weight of Toluene and 20 parts by weight of MEK were added to 100 parts by weight of the hydrophobic polyurethane resin and dispersed for 15 minutes using a homomixer to prepare a coating solution (Viscosity 3,000 to 3,200 cps at 25 ° C). The prepared coating solution was formed into a film having a thickness of 20 μm with a comma knife on a release paper and dried at about 120 ° C. for 1 minute and 30 seconds to prepare a film.
[Experimental Example]
The moisture permeability and water pressure of each of the films prepared in the same manner as in Examples 3 and 4 and Comparative Example 2 were measured by varying the weight of the silicate synthesized in Examples 1 and 2 and Comparative Example 1, ].
Comparative Example 2
(g / m224hr)
1,000
2,200
2,500
(mmH 2 O)
10,000
10,000
10,000
Example 3
(g / m224hr)
4,300
7,700
9,300
(mmH 2 O)
10,000
10,000
10,000
Example 4
(g / m224hr)
4,600
7,800
10,000
(mmH 2 O)
10,000
10,000
10,000
As shown in Table 1, the moisture-permeable tarpaulin made of the polyurethane resin composition for non-swellable moisture-permeable and waterproofing using the surface-treated nanosilica particles according to the present invention has a water pressure of 10,000 mmH 2 O (ISO 0811) or more and a moisture permeability of 7,700 The present invention relates to a high moisture permeable waterproofing cloth which is superior in water resistance and moisture permeability to a conventional high moisture permeable waterproofing cloth and which does not cause swelling due to moisture absorption, , The polyurethane resin composition of the present invention is used in clothing, gloves, socks, hats, shoes, tents, and other articles such as mountaineering clothes, sportswear, casual wear, work clothes, Superior effect can be expected in suppressing moisture penetration into the outside air and preventing moisture from condensation by sweating and moisture condensation to the outside. All.
Therefore, the polyurethane resin composition for non-swellable moisture-permeable and waterproofing polyurethane resin using the surface-treated nanosilica particles of the present invention can be variously substituted, modified and changed without departing from the technical idea of the present invention. Can be used in various applications and forms such as being coated on the surface of a textile product or bonded in a film form.
Claims (7)
The silane compound may be selected from the group consisting of 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, {3-acryloxy propyl trimethoxysilane}, and more preferably,
The polyethylene glycol macromer uses at least one poly (ethylene glycol) methyl ether methacrylate selected from the group consisting of number average molecular weights of 950, 1500 and 4,000,
5 to 15 parts by weight of dimethylformamide (DMF) based on 100 parts by weight of the hydrophobic polyurethane resin; 15 to 25 parts by weight of toluene (Toluene); And a solvent comprising 15 to 25 parts by weight of methylethylketone (MEK), and having a viscosity of 3,000 to 3,200 cps (based on 25 DEG C). The non-swellable polyurethane resin for moisture- Composition.
Wherein the polyurethane resin composition is coated on a release paper to form a moisture permeable waterproofing film having a thickness of 10 to 30 占 퐉. The polyurethane resin composition for non-swelling waterproofing and moistureproofing waterproofing using the surface treated nanosilica particles.
Wherein the moisture permeable protective film of the film type has a water pressure of 10,000 mmH 2 O (ISO 0811) or higher and a moisture permeability of 7,700 g / m 2 24 hrs (JIS L 1099A-1 method) Embedded polyurethane resin composition
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102007392B1 (en) * | 2018-04-27 | 2019-08-05 | 서용성 | Waterborne resin composition containing silicone-modified polyurethane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100909677B1 (en) * | 2008-10-20 | 2009-07-29 | 주식회사 비 에스 지 | Method of preparing non swelling multilayer film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100909677B1 (en) * | 2008-10-20 | 2009-07-29 | 주식회사 비 에스 지 | Method of preparing non swelling multilayer film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102007392B1 (en) * | 2018-04-27 | 2019-08-05 | 서용성 | Waterborne resin composition containing silicone-modified polyurethane and preparation method thereof |
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