KR102092532B1 - Flame retardant water-dispersive polyurethane resin composition for dip coating of suede and its manufacturing process - Google Patents

Abstract

The present invention relates to a flame retardant water-dispersible polyurethane resin composition for impregnation coating of suede, and to a production method thereof. The flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede according to the present invention comprises: (a) 20 to 40 wt% of polyether polyol having weight average molecular weight of 3,000 or more; (b) 15 to 30 wt% of flame retardant diol; (c) 1 to 2 wt% of a diol-based chain extender; (d) 22 to 28 wt% of isophoron diisocyanate (IPDI); (e) 0.4 wt% of catalyst; (f) 1.7 to 2.8 wt% of 2,2-bis (hydroxymethyl)butyl acid (DMBA); (g) 3 to 8 wt% of hydrophilic polyol; (h) 1 to 3 wt% of a neutralizing agent; (i) 0.7 to 1.1 wt% of a hydrazine monohydrate chain extender; (j) 5 to 9 wt% of a non-reactive silicone additive; (k) 0.4 wt% of an antioxidant; and (l) 0.4 wt% of a No_x inhibitor in a proportion. The flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede produced through the present invention has excellent flame retardancy without adversely affecting physical properties by applying a reactive flame retardant (flame retardant diol).

Description

Flame Retardant Water Dispersion Polyurethane Resin Composition for Impregnated Coating and Method for Manufacturing The Same FLAME RETARDANT WATER-DISPERSIVE POLYURETHANE RESIN COMPOSITION FOR DIP COATING OF SUEDE AND ITS MANUFACTURING PROCESS}

The present invention relates to a flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede and a method for manufacturing the same, and more specifically, slip resistance, resistance to slip by applying a water-dispersible polyurethane (PUD) of a solvent-free type having excellent flexibility properties to suede It relates to a flame-retardant water-dispersible polyurethane resin composition for impregnating coating of suede having excellent properties such as flexibility and yellowing resistance, and a method for manufacturing the same.

In general, 'suede' is a fabric made by imitating lamb, goat, and calf skins with tannic or formic acid aldehyde, and gently treating the back to a velvety surface or by imitating it. Esau is better known as 'taxation' than suede, and, like leather, is less susceptible to moisture and water. However, it is much more water resistant than normal leather and can be restored unless it is completely wet and messed up. The popular belief that suede is vulnerable to water is because it is not well known how to manage suede.

Suede materials are commonly used for clothing, gloves, belts, handbags, and shoe skins, and products that are coated with urethane resin on suede to improve the elasticity, filling, and feel of suede fabrics are manufactured. As most solvent-based urethane resins are used as solvents, environmental pollution and harmfulness to humans due to volatile organic compounds (VOCs) generated during the manufacturing process or in products are becoming a problem.

For the above reasons, when using a water-dispersible polyurethane resin (PUD) that does not use a solvent for the coating of suede, it can be manufactured as an environmentally friendly product, but when using PUD for impregnating coating of suede, it has poor flexibility and bending. A lot of problems such as deterioration of strength and yellowing have occurred.

In the conventional manufacturing process (prepolymer method) of the water-dispersible polyurethane (PUD), a polyol, a dispersing agent (ionizing agent), a neutralizing agent, a chain extender of a prepolymer, and an isocyanate are mixed and reacted at a high temperature to prepare a prepolymer, followed by high speed. A prepolymer is added to the stirred water to disperse it, and then a chain extender is added and the molecular weight is adjusted through polymerization of the dispersed prepolymer to synthesize a water-dispersible polyurethane resin having an appropriate molecular weight.

In order to solve the problems of the conventional water-dispersible polyurethane resin (PUD), Republic of Korea Patent Publication No. 10-0812635 (Hyundai Hichem Co., Ltd.) polycarbonate diol (PCD) and anion-imparting functional diol to 100 to 120 ℃ Heating to dissolve the anion-imparting functional diol in polycarbonate diol (PCD), removing water, adding a diisocyanate-based compound, nitrogenating the reactor interior, and introducing a neutralizing agent Polymerizing the prepolymer through a process; Polymerizing the polycarbonate polyurethane through a process of forcibly dispersing the prepolymer in a disperser containing deionized water (DIW) and adding an extender; It is said that an environmentally friendly water-dispersible PC / PU polyurethane resin having excellent physicochemical properties can be obtained from a method for producing a water-dispersible polycarbonate polyurethane resin comprising filtering using a filter such as a nonwoven fabric or cotton cloth.

In addition, the registered patent publication No. 10-0969046 (Hyundai Motor Co., Ltd.) is a chain extender and 1,6-hexamethylene diisocyanate, 4,4-dicyclohexmethane diisocyanate, isophorone diisocyanate, and mixtures thereof. A first step of reacting a diisocyanate compound which is an aliphatic compound selected from 1: 2.5 to 3 weight ratio to prepare a hard segment at the end of the isocyanate group; 100 parts by weight of the hard segment; 295 to 310 parts by weight of an ether type or ester type polyol; And reacting 65 to 80 parts by weight of the diisocyanate compound to prepare a prepolymer I of a hydroxyl group terminal containing a soft segment; 100 parts by weight of the prepolymer I; 2 to 3 parts by weight of a diol having a carboxyl group which is dimethylol propionic acid, dimethylol butanoic acid, or a mixture thereof; And reacting 2 to 4 parts by weight of diisocyanate compound to prepare prepolymer II; And dispersing the prepolymer II to produce a water-dispersible polyurethane resin having a hard segment at the center of the chain and a soft segment at the end of the chain. The solid content is 30 to 45% by weight. A method for producing a water-dispersible polyurethane resin is disclosed.

And when looking at the registered patent publication No. 10-1609175 (Intermaru Industries Co., Ltd.), there is no discharge of organic solvent, good processability, good coating properties, water-resistant polyurethane impregnated suede tank excellent in abrasion resistance, heat resistance, light resistance, wash fastness To manufacture knitted fabrics in an environmentally friendly manner, after elution, a water-soluble polyester-based island-in-the-sea yarn with a single yarn fineness of 0.01 to 0.1 denier and a high-shrink polyester polyester of 20 to 30 denier / 12 pillars with a non-shrinkage rate of 30 to 50% After knitting an interlock knitted fabric having a knitting weight of 260 to 290 g / yd and a thickness of 0.4 to 0.6 mm with an interlaced yarn of filament, refining and shrinking in hot water at 60 to 100 ° C to divide the polyester island-in-the-sea yarn, followed by dyeing and freeing. Setting, brushing, mixing 15 to 35% of water-dispersible polyurethane with 100 parts by weight of acrylic thickener 0.1 to 5 parts by weight, silicone softener 0.1 to 10 parts by weight, water 400 to 500 parts by weight, mixing for 60 to 120 minutes And it is then impregnated with a 10% to 20% pick-up rate in a water-soluble polyurethane adjusted to a viscosity of 1,000 ~ 1,500cps, heat treatment, buffing the method of manufacturing a waterborne polyurethane impregnated suede, knitted, characterized in that to complete the base.

On the other hand, the applicant of the patent application No. 10-1860708 (Bix Co., Ltd.) (a) organosilicon compound 3 to 20% by weight, (b) diisocyanate 12 to 40% by weight, (c) catalyst 0.5 to 2 Weight%, (d) 15 to 51% by weight of polycarbonate diol, (e) 15 to 67% by weight of polyether polyol, (f) 2,2-bis (hydroxymethyl) butyl acid (DMBA) 60 to 90 parts by weight of an ionic prepolymer composed of 2 to 10% by weight; (h) 60 to 89% by weight of a hydrophilic polyol, (i) 10 to 39% by weight of a diisocyanate, (j) 10 to 40 parts by weight of a nonionic prepolymer composed of 0.5 to 2% by weight of a catalyst; (k) 1 to 4 parts by weight of a neutralizing agent; (l) An aqueous dispersion polyurethane resin composition for impregnating coating of suede, which comprises 2 to 8 parts by weight of an amine chain extender, and a method of manufacturing the same.

However, although the water-soluble or water-dispersible polyurethane resin (PUD) according to the above-described method may achieve an environmentally friendly function to some extent, a coating expressed when dip coating the suede using such PUD is coated. Suede softness (Material softness) shows a stiff feel as the thickness of the suede fabric increases to 1.0 mm or more and the coating weight increases, showing a lower value. In addition, recently, as the utilization of suede has been increased for applications such as gloves, shoes, and materials for vehicles, flame retardancy is additionally required in addition to the existing demands. By this, flame retarding is mandatory.

Accordingly, as a general method for imparting flame retardancy to the water-dispersible polyurethane for suede, a method of post-fixing a certain amount of a phosphorus-based flame retardant such as triaryl phosphate or a halogen-based flame retardant is used when mixing the polyurethane compound for coating. In the case of the above method, the flame retardant is released to the surface over time to seriously degrade work efficiency or change the color of the fabric in post-processing. These flame retardants have a low molecular weight, and when the temperature inside the vehicle increases, such as in summer, they diffuse into the air, and the flame retardancy of the product decreases, and they also release harmful components such as hydrogen halide.

Meanwhile, in the present invention, a small amount of a hydrophilic polyol and a diol-based chain extender is applied to the polyether polyol to improve suede flexibility, and a non-reactive silicone additive is used to minimize friction between the impregnated fibers and thus to the suede fabric. It is possible to achieve excellent softness (Material softness), and also by applying a reactive flame retardant, it is a flame retardant water-dispersible polyurethane resin composition that has excellent penetration properties to suede without changes in physical properties, and has excellent touch, flex resistance, and yellowing resistance during coating. It was developed and completed the present invention.

Republic of Korea Registered Patent Publication No. 10-0812635 (Announcement date of March 13, 2008) Republic of Korea Registered Patent Publication No. 10-0969046 (Announcement date of July 09, 2010) Republic of Korea Registered Patent Publication No. 10-1609175 (Announcement date April 6, 2016) Republic of Korea Registered Patent Publication No. 10-1860708 (announcement date May 24, 2018)

The object of the present invention was to apply a small amount of a hydrophilic polyol and a diol-based chain extender to a polyether polyol having a molecular weight of 3,000 or more to improve the flexibility of the hydrophilic suede, and also use a non-reactive silicone additive for improving slip properties between coated filaments. Therefore, it is possible to achieve excellent softness (Material softness) even in a suede fabric of 3.0 mm or more, and by applying a reactive flame retardant such as a flame-retardant diol, the property change is minimized, but the penetration property to the suede is excellent, and the feel of coating (slip property), It is to provide a flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede with optimized properties such as flexibility and yellowing resistance, and a method for manufacturing the same.

The flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede according to the present invention comprises: (a) 20 to 40% by weight of a polyether polyol having a weight average molecular weight of 3,000 or more; (b) 15 to 30% by weight of flame retardant diol; (c) 1 to 2% by weight of a diol-based chain extender; (d) 22 to 28% by weight of isophorone diisocyanate (IPDI); (e) 0.4% by weight of catalyst; (f) 1.7 to 2.8% by weight of 2,2-bis (hydroxymethyl) butyl acid (DMBA); (g) 3 to 8% by weight of hydrophilic polyol; (h) 1-3% by weight of neutralizing agent; (i) Hydrazine monohydrate chain extender 0.7-1.1 wt%; (j) 5 to 9% by weight of a non-reactive silicone additive; (k) 0.4% by weight of antioxidants; (l) Nox inhibitor is characterized by being composed in a proportion of 0.4% by weight.

According to a preferred embodiment of the present invention, the polyether polyol (a) is polypropylene glycol (Polypropylene glycol, PPG) having a weight average molecular weight of 3,000 to 4,000, and the flame-retardant diol (b) is tetrabromophthalate diol (Tetrabromophthalate Diol) , The diol-based chain extender (c) is applied to 1,4-butanediol (1,4-butandiol), the hydrophilic polyol (g) is polyethylene glycol (Polyethylene glycol, PEG), the non-reactive silicone additive ( j) is an emulsion-type polydimethylsiloxane (Polydimethylsiloxane) containing a cyclic dimethylsiloxane tetramer (Cyclic dimethylsiloxane tetramer) is applied.

The manufacturing method of the flame retardant water-dispersible polyurethane resin composition for impregnating coating of the suede is (a) 20 to 40% by weight of a polyether polyol having a weight average molecular weight of 3,000 or more, (b) 15 to 30% by weight of a flame-retardant diol, (c) diol After adding 1 to 2% by weight of the chain extender, (e) 0.4% by weight of the catalyst, and (f) 1.7 to 2.8% by weight of 2,2-bis (hydroxymethyl) butyl acid (DMBA) at a temperature of 45 ° C , (d) Isophoron diisocyanate (IPDI) 22-28 wt% is added and reacted at a temperature of 90 ° C. for 3 hours to synthesize a first-stage prepolymer, and then (g) hydrophilic polyol 3 to 3 ~ A first step of preparing a prepolymer by adding 8% by weight and reacting for 1 hour to synthesize a two-stage prepolymer and then cooling it to 60 to 70 ° C; After pre-dispersing the prepared prepolymer in deionized water maintained at 20 ~ 30 ℃ (h) 1 ~ 3% by weight of a neutralizing agent at high speed, (i) Hydrazine monohydrate (Hydrazine monohydrate) chain extender 0.7 ~ 1.1% by weight A second step of adding and subdividing% in accordance with the remaining NCO%, followed by chain extension reaction, to prepare a polyurethane resin; It consists of a third process of adding (j) 5 to 9% by weight of a non-reactive silicone additive, (k) an antioxidant of 0.4% by weight, and (l) 0.4% by weight of a Nox inhibitor to the prepared polyurethane resin.

The flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede produced through the present invention is coated with a small amount of a hydrophilic polyol and a diol-based chain extender to a polyether polyol having a molecular weight of 3,000 or more, and the suede fabric coated therewith is a non-reactive silicone additive. It not only has excellent flexibility (Material softness) than the conventional PUD used, but also has excellent tactile, flexural, and yellowing resistance characteristics even in suede fabrics of 3.0 mm or more, and it also has excellent properties without adversely affecting physical properties by applying a reactive flame retardant (flame-retardant diol). It has the effect of having flame retardancy.

Hereinafter, a flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede according to the present invention will be described, which is intended to be illustrated to such an extent that it can be easily carried out by a person having ordinary knowledge in the technical field to which the present invention pertains. However, this does not mean that the technical spirit and scope of the present invention is limited.

The flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede according to the present invention is basically: (a) 20 to 40% by weight of a polyether polyol having a weight average molecular weight of 3,000 or more; (b) 15 to 30% by weight of flame retardant diol; (c) 1 to 2% by weight of a diol-based chain extender; (d) 22 to 28% by weight of diisocyanates of isophorone diisocyanate (IPDI) type; (e) 0.4% by weight of catalyst; (f) 1.7 to 2.8% by weight of 2,2-bis (hydroxymethyl) butyl acid (DMBA); (g) 3 to 8% by weight of hydrophilic polyol; (h) 1-3% by weight of neutralizing agent; (i) Hydrazine monohydrate chain extender 0.7-1.1 wt%; (j) 5 to 9% by weight of a non-reactive silicone additive; (k) 0.4% by weight of antioxidants; (l) Nox inhibitor 0.4% by weight.

The method for preparing the flame-retardant water-dispersible polyurethane resin composition, first (a) 20 to 40% by weight of a polyether polyol having a weight average molecular weight of 3,000 or more, (b) 15 to 30% by weight of a flame-retardant diol, (c) diol chain extension After mixing 1 to 2% by weight, (e) 0.4% by weight of catalyst, (f) 2,2-bis (hydroxymethyl) butyl acid (DMBA) 1.7 to 2.8% by weight at a temperature of 45 ° C., (d ) Isophoron diisocyanate (IPDI) 22-28 wt% was added and reacted at a temperature of 90 ° C. for 3 hours to synthesize a first-stage prepolymer, and then (g) 3-8 wt% hydrophilic polyol to the prepolymer. After adding and reacting for 1 hour to synthesize a two-stage prepolymer, a process of cooling to 60 to 70 ° C is performed to prepare a prepolymer.

The polyether polyol (a) used in the prepolymer manufacturing process may be polypropylene glycol, polytetramethylene glycol, and one or more polyether polyols derived therefrom. Preferably, by using polypropylene glycol having a weight average molecular weight of 3,000 to 6,000, it is possible to extremely increase the material softness characteristics, and a flame retardant diol having a relatively low molecular weight (Mw = 400 to 700) added thereafter. Even when applying (b), sufficient flexibility can be exhibited.

In addition, the flame-retardant diol (b) may be used for various reactive flame retardants, usually phosphorus-based and bromine-based, but in the present invention, tetrabromophthalate diol (Tetrabromophthalate Diol) was selected, which is compared to the commonly used flame retardant. It shows good coating properties and excellent flame retardancy without deteriorating flexural strength as well as flexibility. However, when the flame retardant is used in an amount of less than 15% by weight, sufficient flame retardancy is not exhibited, and when it is used in excess of 30% by weight, the viscosity of the prepolymer is high, making it difficult to adjust the dispersion and reaction process, as well as low flexibility and flexural strength, especially low molecular weight. It is difficult to maintain adequate flexibility.

The diol-based chain extender (c) includes monoethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butandiol, 1,4-butandiol, 1 Glycols such as, 6-hexane diol can be used, but 1,4-butanediol (1,4-butandiol) in a proportion of 1 to 2% by weight based on the total weight of the resin composition can be used. It was found to be the most suitable in terms of flowability, mechanical strength and material softness of the resin.

In addition, the isophorone diisocyanate (IPDI) (d) may be an aliphatic isocyanate type such as tetramethyl xylene diisocyanate, but these diisocyanates are sticky during dip coating. Considering the tackiness and slipperiness between the fabric filaments and the flexibility and tactile feel, the use of isophorone diisocyanate has been studied as more preferable, and the reaction ratio of the diisocyanate to the reactive hydrogen atom compound (OH / NCO) Ratio) is most preferably used in a value of 1.0 to 1.9 in an equivalent ratio, more preferably 1.0 to 1.2.

As the catalyst (e), most catalysts applied to PUD can be used. Representatively, organic metal catalysts such as bismuth-based catalysts, tertiary amine-based catalysts, and dibutyltin dilaurate are used. Can be used. In addition, 2,2-bis (hydroxymethyl) butyric acid (DMBA) (f), which is used as an ionizing agent, was most appropriate when considering dispersibility when it was contained within 1.7 to 2.8 wt% based on the total weight of the resin composition. .

In addition, it was investigated that the use of polyethylene glycol (PEG) as the hydrophilic polyol (g) is most suitable for resin dispersibility. The hydrophilic polyol (g) acts as an emulsifier, and when diluting the water-dispersion type resin, the dispersion resin is entangled into larger particles and the dispersion degree is adjusted so that each filament part of the suede can be coated with a shape such as a bonding point. Through this, it is possible to manufacture a water-dispersible polyurethane resin having superior flexibility and simultaneously expressing the elasticity of urethane compared to suede fabrics that have been impregnated after diluting the existing water-dispersible polyurethane resin.

When the hydrophilic polyol (g) as described above is directly applied, it is added in an amount in the range of 3 to 8% by weight based on the total amount of the water-dispersible polyurethane resin composition. When it exceeds 8% by weight, the resin becomes easily gelled during the chain extension reaction because the resin is entangled when dispersed.

Next, after pre-dispersing the prepared prepolymer in deionized water maintained at 20 to 30 ° C. (h) 1 to 3 wt% of a neutralizing agent at high speed, (i) Hydrazine monohydrate chain extender 0.7 ~ 1.1% by weight is added to the remaining NCO% in small portions, followed by a chain extension reaction to undergo a second process to prepare a polyurethane resin. At this time, the temperature of the water (deionized water) is maintained at 30 ° C or less to cause side reaction with water. Should be minimized.

Triethylamine (TEA) may be used as the neutralizing agent (h), and the hydrazine monohydrate chain extender (i) used herein is an aliphatic polyamine diethylene tree having 2 to 36 carbon atoms. Polyamines such as amine, dipropylene triamine, dihexylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine or 1,3- or 1,4-diaminocyclohexane, 4 Any one or more chain extenders selected from, 4'- or 2,4'-dicyclohexylmethane diamine and isophorone diamine may be used, but flexibility when using hydrazine monohydrate as in the present invention It was confirmed that it is possible to prepare a water-dispersible polyurethane resin having good dispersibility while maintaining well.

Finally, (3) non-reactive silicone additives (5) to 9% by weight of the prepared polyurethane resin, (k) 0.4% by weight of an antioxidant, and (l) flame retardant water through a third step of adding 0.4% by weight of an antioxidant. A dispersed polyurethane resin composition is prepared, wherein the non-reactive silicone additive (j) is a silicone oil emulsion type capable of imparting slip and anti-blocking effects such as TEGO® Glide 482. It is preferable to use an additive of, and among them, it has been investigated that it is most preferable to apply an emulsion type polydimethylsiloxane containing a cyclic dimethylsiloxane tetramer. It was confirmed that the non-reactive silicone additive (j) does not sufficiently exhibit flexibility when used at less than 5% by weight, and does not significantly change flexibility when used at more than 9% by weight.

In addition, in the present invention, (k) an antioxidant of 0.4% by weight and (l) Nox of an antioxidant of 0.4% by weight were used to minimize the reactivity of the residual amine groups, thereby minimizing yellowing to maintain a continuous primary color. The antioxidant (k) is triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] (Triethylene glycol bis [3- (3-t-butyl-4- hydroxy-5-methylphenyl) propionate]), and the Nox inhibitor (l) is 1,6-hexamethylene bis (N, N-dimethylsemicarbazide) (1,6-Hexamethylene bis (N, N-dimethylsemicarbazide)) It is preferred to use.

When the polyurethane resin prepared through the present invention is used for impregnating coating, distilled water is mixed and diluted in a weight ratio of 1: 1 to 5 compared to the prepolymer prepared through the first process, so that the impregnation liquid solid content is 10% by weight. It is preferable to adjust the PUD impregnation solution to be inside and outside, and poly obtained by applying a conventional inorganic salt-based gelling agent within a range of 3 to 7 parts by weight based on 100 parts by weight of the prepolymer in order to adjust the feel and fill of the coated resin Suede may be impregnated with a urethane resin solution to produce a product.

The non-woven fabric used in the impregnation process in the present invention is not particularly limited to its type, but PET single-sided / double-sided and CDP single-sided / double-sided suede having a thickness of 1.0 to 1.3 mm are most suitable. Suede was impregnated with the water-dispersible polyurethane resin solution developed as described above for 30 seconds and then mangleed with a gapless 1 kgf, and after impregnation treatment, dried at 100 ° C. for 4 minutes and 30 seconds to prepare a suede material.

Hereinafter, an example in which a flame retardant water-dispersion-type polyurethane resin composition for impregnating coating of suede according to the present invention is tested will be described, but a person skilled in the art to which the present invention pertains may easily perform The present invention will be described through preferred embodiments.

[Example 1]

Preparation of prepolymer

After mixing 924 g of polypropylene glycol, tetrabromophthalatediol-based flame retardant 720 g, 1,4-butanediol 42 g, catalyst 7 g, and DMBA 52 g at a temperature of 45 ° C. in a 4-neck 1 L reactor, 784 g of isophorone diisocyanate was added and 90 After reacting for 3 hours at a temperature of ℃ to synthesize a first-stage prepolymer, 199 g of polyethylene glycol was added thereto to synthesize a second-stage prepolymer through a process of reacting for 1 hour, and then cooled to 65 ° C. to prepare a final prepolymer.

Dispersion and chain extension

After preparing 692 g (23 ° C.) of deionized water in a 4-neck 1 L reactor, 40 g of TEA was added thereto, stirred for 30 minutes, and while maintaining the water temperature at 20 to 25 ° C., 300 g of the finally prepared prepolymer was added to the deionized water mixture. And dispersion within 30 minutes. Here, 24 g of hydrazine monohydrate is diluted in 27 g of deionized water and added in small portions to carry out a chain extension reaction, and when the remaining -NCO group disappears, the reaction is terminated. 224 g of non-reactive silicone additives, 12 g of antioxidants, and 12 g of NOx inhibitors were added to the polyurethane resin thus obtained to obtain a water-dispersible polyurethane resin composition having a solid content of 30% by weight and a viscosity of 2,000 cps / 25 ° C.

Suede impregnated coating

100 g of water-dispersed polyurethane resin composition obtained through the above process is diluted in 400 g of distilled water to prepare a blending solution, and impregnated into a PET single / double-sided, CDP single-sided / double-sided type suede having a thickness of 1.0 mm or more in this solution for 30 seconds. After the pressing, a pressing process using a mangle was carried out 2 to 5 times, and then, under the temperature of 80 ° C, 100 ° C, 120 ° C, and 150 ° C, each was dried for 30 seconds to 5 minutes to prepare a suede material.

[Example 2]

Example 2 is an example except that the amount of the tetrabromophthalate diol flame retardant is reduced to 15% of the solid content and the amount of DMBA and 1,4-butandiol is increased and the amount of the PEG and silicone additives is reduced to adjust flexibility. A water-dispersible polyurethane resin composition was obtained in the same manner as in 1, and a suede material was also prepared in the same manner as in Example 1 for the impregnation coating treatment of suede.

[Comparative Example 1]

Comparative Example 1 is an example except that the amount of the tetrabromophthalate diol flame retardant is increased to 30% of the solid content, and the amount of DMBA, 1,4-butandiol, PEG, and silicone additives is adjusted to an amount similar to Example 2 A water-dispersible polyurethane resin composition was obtained in the same manner as in 1, and a suede material was also prepared in the same manner as in Example 1 for the impregnation coating treatment of suede.

[Comparative Example 2]

Comparative Example 2 is the same method as in Example 1, except that the amount of the flame retardant is reduced to 10% of the solid content and the amounts of DMBA, PEG, hydrazine monohydrate, and silicone additives are adjusted to similar amounts to Example 2. As a result, a water-dispersible polyurethane resin composition was obtained, and a suede material was prepared in the same manner as in Example 1 for the impregnation coating treatment of suede.

The mixing amounts of the constituents in the water-dispersible polyurethane resin compositions respectively carried out in Examples 1 and 2 and Comparative Examples 1 and 2 (unit: g) are shown in Table 1 below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Polyether polyol 924 1220 843 1328 Flame retardant 720 459 907 321 Diol chain extender 42 56 39 61 catalyst 7 10 7 11 Ionizing agent 52 82 57 89 Diisocyanate 784 781 831 762 Hydrophilic polyol 199 164 113 179 corrector 40 40 40 40 Chain extender 24 31 22 34 Silicone additives 224 165 159 179 Antioxidant 12 16 11 18 Nox inhibitor 12 16 11 18

[Experimental Example]

The results of measuring the physical properties of the water-dispersible polyurethane resin compositions respectively carried out in Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 2 below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Tensile strength (㎏f / ㎠) 350 300 400 250 Elongation (%) 400 500 350 550 Material softness (㎜) 2.8 3.5 2.0 3.7 Flexural strength (more than times) 100,000 100,000 100,000 100,000 Flame retardant SE SENBR SE B

* Tensile strength, elongation: Measured by ASTM E252 method

* Material Softness: Measured by ISO 17235 method

* Flexural strength: measured by DIN53343 method

* Flame retardancy: measured by ISO 3795 method

* Flame retardant standard

-SE: The light is on, but the light goes out before the mark (38 mm) of the “start”.

-SENBR: Combustion starts, the time is measured at the “start point”, it turns off before 60 seconds, and the carbonization distance is less than 50 mm.

-B: The fire starts to ignite at the 'start point' and continues to burn until after the mark (254mm) of the 'end point'.

As in the measurement results, as the content of the flame retardant increases (Example 1, Comparative Example 1), the tensile strength of the film increases significantly and flame retardancy improves. However, the material softness is reduced to 3 mm or less, and in Comparative Example 1, it is unsuitable for use at a level of 2.0 mm. To improve this, the amount of PEG and silicone additives is increased and the amount of dispersant and chain extender is adjusted. In the case of Example 1, a product exhibiting a relatively good flexibility value of 2.8 mm or more can be manufactured. When high flexibility is required, it is considered that the compounding conditions of Example 2 satisfying the flame retardancy of SENBR grade are most suitable.

Therefore, the flame-retardant water-dispersible polyurethane resin composition prepared according to the present invention has relatively good flexibility (Material softness) and flexural strength when impregnated coating of suede, and can also express flame retardancy, so that it does not depart from the technical spirit of the present invention. It is an eco-friendly material that can be applied to materials such as clothing, gloves, vehicle materials, and shoe skins that require surface treatment within, and can be used in various uses and shapes.

Claims (5)

(a) 20 to 40% by weight of a polyether polyol having a weight average molecular weight of 3,000 or more;
(b) 15 to 30% by weight of flame retardant diol;
(c) 1 to 2% by weight of a diol-based chain extender;
(d) 22-28% by weight of isophorone diisocyanate (IPDI);
(e) 0.4% by weight of catalyst;
(f) 1.7 to 2.8% by weight of 2,2-bis (hydroxymethyl) butyl acid (DMBA);
(g) 3 to 8% by weight of hydrophilic polyol;
(h) 1-3% by weight of neutralizing agent;
(i) Hydrazine monohydrate chain extender 0.7-1.1 wt%;
(j) 5 to 9% by weight of a non-reactive silicone additive;
(k) 0.4% by weight of antioxidants;
(l) 0.4% by weight of Nox inhibitor;
A flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede, characterized in that it is composed of a ratio of. According to claim 1,
The polyether polyol (a) is polypropylene glycol (PPG) having a weight average molecular weight of 3,000 to 4,000, and the flame retardant diol (b) is tetrabromophthalate diol (Tetrabromophthalate Diol), the diol chain extender (c) ) Is a flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede, characterized in that 1,4-butanediol (1,4-butandiol) is applied. According to claim 1,
The hydrophilic polyol (g) is a flame retardant water-dispersible polyurethane resin composition for impregnating coating of suede, characterized in that it is polyethylene glycol (Polyethylene glycol, PEG). According to claim 1,
The non-reactive silicone additive (j) is a flame retardant water-dispersible polyurethane resin for impregnating coating of suede, characterized in that an emulsion type polydimethylsiloxane containing a cyclic dimethylsiloxane tetramer is applied. Composition. (a) 20 to 40% by weight of a polyether polyol having a weight average molecular weight of 3,000 or more, (b) 15 to 30% by weight of a flame retardant diol, (c) 1 to 2% by weight of a diol chain extender, (e) 0.4% by weight of a catalyst, (f) After mixing 1.7 to 2.8% by weight of 2,2-bis (hydroxymethyl) butyl acid (DMBA) at a temperature of 45 ° C., (d) Isophoron di-isocyanate (IPDI) 22 ~ After adding 28% by weight and reacting at a temperature of 90 ° C. for 3 hours to synthesize a first-stage prepolymer, (g) adding 3 to 8% by weight of a hydrophilic polyol to the prepolymer and reacting for 1 hour to synthesize a second-stage prepolymer. A first process of preparing a prepolymer in a process of cooling to 60 to 70 ° C. after one;
After pre-dispersing the prepared prepolymer in deionized water maintained at 20 ~ 30 ℃ (h) 1 ~ 3% by weight of a neutralizing agent at high speed, (i) Hydrazine monohydrate (Hydrazine monohydrate) chain extender 0.7 ~ 1.1% by weight A second step of adding and subdividing% in accordance with the remaining NCO%, followed by chain extension reaction, to prepare a polyurethane resin;
A third step of adding (j) 5 to 9% by weight of a non-reactive silicone additive to the prepared polyurethane resin, (k) 0.4% by weight of an antioxidant, and (l) 0.4% by weight of a Nox inhibitor;
Method for producing a flame retardant water dispersion polyurethane resin composition for impregnating coating of suede, characterized in that consisting of.