KR101972774B1 - Reactive polyurethane hotmelt adhesives having the non-swelling property and producing method of coating textile using the same - Google Patents

Abstract

The present invention relates to a reactive polyurethane hot melt adhesive having non-swelling properties and a process for producing a coated fabric using the same, wherein the reactive polyurethane hot melt adhesive comprises (a) ethylene oxide / tetrahydrofuran (EO / THF ) Composed of an ethylene oxide / tetrahydrofuran block copolymer (EO / THF block copolymer) having a number-average molecular weight of 1,000 to 2,000 and a hydroxyl value of 56 to 110 mg KOH / g, the molar ratio being 5/5 10 to 40% by weight of polyol; (b) a hydrophobic polyether polyol composed of any one selected from the group consisting of polypropylene glycol having a number average molecular weight of 1,000 to 2,000 and hydroxyl group of 56 to 110 mg KOH / g, polybutylene glycol and polytetramethylene glycol, 25% by weight; (c) 1 to 3% by weight of a reactive silicone oil having a number average molecular weight of 3,000 to 5,000; (d) at least one diol selected from 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, ethylene glycol, and hexanediol is reacted with adipic acid or isophthalic acid 30 to 60% by weight of a polyester polyol prepared by blending a polyester polyol having a number average molecular weight of 2,000 to 4,000 and a hydroxyl value of 25 to 55 mgKOH / g with polycaprolactone (PCL) at a weight ratio of 1: 0.8 to 1.2; (e) 15 to 30% by weight of a diisocyanate; (f) 0.5-1 wt% of a hygroscopic agent; (g) 1 to 5% by weight of an adhesive reinforcing agent; (h) 0.1 wt% of the catalyst, the viscosity is 4,000-12,000 cps / 100 deg. C, and the NCO content is 1.8-3.0 wt%.
The reactive polyurethane hot melt adhesive is prepared by mixing a hydrophilic polyether polyol prepared by using an ethylene oxide / tetrahydrofuran block copolymer (PO / THF block copolymer) having a number average molecular weight of 1,000 to 2,000 and a polyester polyol, By providing non-swelling properties, surface characteristics and water-resistant adhesive strength are improved. To this end, a reactive silicone oil for enhancing non-expansion properties, a moisture absorber for adjusting reaction rate, and an adhesive reinforcing agent for improving adhesion , The moisture permeability and adhesive strength are excellent, and storage and processing stability are improved. In addition, since it is an environmentally friendly polyurethane adhesive of 100% solids which does not use a solvent, it is adhered to a fiber material by thermal melting, so that a coating having excellent properties such as adhesive strength and peel strength, There is an advantage that fabrics can be manufactured.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a reactive polyurethane hot-melt adhesive having a non-expanding property and a method of manufacturing a coated fabric using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a reactive polyurethane hot melt adhesive having a non-swelling property and a method for producing a coated fabric using the same. More specifically, the present invention relates to a reactive polyurethane hot- It contains moisture absorber for adjusting the reaction rate and adhesion enhancer for improving the adhesion speed, and is excellent in moisture permeability and adhesive strength, and has excellent storage and processing stability. A reactive polyurethane hotmelt adhesive for coating a textile material having good non-swelling properties and a process for producing a coated fabric using the same.

Recently, environmental issues have become an important issue, and development of products that minimize environmental pollution in various fields is required. In response to these demands, reactive hot melt adhesives are 100% solids-free, eco-friendly products that do not use solvents and are bonded to the adherend after heat fusing without evaporation of the solvent and then exhibit excellent adhesion by moisture in the air.

The reactive hot melt adhesives described above are superior to conventional hot melt adhesives because they exhibit adhesive strength and structural strength by chemical cross-linking, and are easily applied to a variety of materials such as automotive, construction, and clothing . As a result, there is an increasing need to improve the interest and characteristics of hot melt materials, and as outdoor activities increase, there is a growing demand for improved functionality in the open air.

When the hot-melt adhesive is applied, the moisture permeable material is bonded to the functional membrane by using a dot roll or a gravure roll, etc. However, the moisture permeability is reduced due to the hot melt used at this time, and the application of the hot melt adhesive is restricted.

Since hot melt adhesives are applied by melting by heat, they are increasingly used as eco-friendly adhesives that do not use volatile organic solvents. In recent years, efforts have been made to prevent global warming in addition to volatile organic compounds, which are harmful to the human body. Are being institutionalized in terms of environmental protection. As part of the global efforts of these countries, the use of resins with low carbon dioxide emissions, ie low LCA (Life Cycle Assessment) values, is required.

The hotmelt adhesive is a solid material at room temperature, but when it is heated, it melts in the fluid state and has an adhesive force to the adherend. When the hotmelt adhesive in the molten state is cooled, it returns to solid form and restores cohesion. The adhesive strength is influenced by the penetration effect of the liquid adhesive flowing through the holes or irregularities on the surface to increase the adhesive strength. To use this effect well, the hot melt adhesive needs to have sufficient flowability when melted. And is used by melting at a high temperature. However, the reactive hot-melt adhesive used in the present invention absorbs moisture after application to the adherend material and has a chemical bonding force in the hot-melt adhesive, so that it has excellent thermal stability and mechanical strength as well as conventional hot-melt adhesives.

Conventional general purpose hot-melt adhesives mainly consist of ethylene vinyl acetate (EVA) as a main component, and are composed of a tackifier for improving adhesion and a wax for lowering viscosity. As the ethylene vinyl acetate, the proportion of vinyl acetate is generally about 20 to 40% by weight. As the pressure-sensitive adhesive, there are used gum rosin, rosin ester, C5 petroleum resin, C9 petroleum resin, coumarone resin, acrylic denatured petroleum resin, As the wax, paraffin wax, polyethylene wax, polypropylene wax and the like are used. However, if the compatibility of the wax and the ethylene vinyl acetate is poor, the viscosity can not be effectively lowered, and phase separation may occur at the use temperature, which may significantly decrease the adhesive strength and cause difficulties in having the function of the adhesive.

In order to solve the problems of such a hot-melt adhesive, Korean Patent Laid-Open Publication No. 10-2008-0088628 discloses a polyurethane resin composition containing a urethane prepolymer obtained by reacting a polyol (A) and a polyisocyanate (B) (A1) in an amount of 40% by mass to 80% by mass, polytetramethylene glycol (a2) in an amount of 5% by mass to 40% by mass, and a polycarboxylic acid containing an aliphatic polycarboxylic acid and an aromatic polycarboxylic acid And a polyester polyol (a3) obtained by reacting a polyether polyol obtained by adding an alkylene oxide to bisphenol A and 5% by mass to 40% by mass of the polyester polyol (a3), and a laminated sheet using the moisture-curable polyurethane hot- According to this adhesive agent, washing under repeated harsh washing conditions is repeated without deteriorating the soft feeling of the laminated sheet Even though it could maintain the excellent adhesion strength.

Korean Patent Laid-Open Publication No. 10-2010-0041692 discloses a polyester polyol (a-1) obtained by reacting an alkylene oxide-added polyol with bisphenol A, an aliphatic polycarboxylic acid with an aromatic polycarboxylic acid, a crystalline polyester (A) containing polyol (a-2) and polyoxyethylene glycol (a-3) having a number average molecular weight of 2000 to 25000 and polyisocyanate (B) The present invention relates to a polyurethane hot melt adhesive, a laminated body using the same, and a moisture permeable film, and it is described that the polyurethane hot melt adhesive can be suitably used for the production of sportswear, raincoats, shoes, firefighter uniforms, military uniforms and the like.

Korean Patent Laid-Open No. 10-2011-0022764 discloses an acrylic resin, a polyurethane resin, a polyester resin, a toluene diisocyanate trimer (TDI Trimer), a cyclohexylmethane diisocyanate (H ₁₂ MDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HMDI) and polypropylene glycol (PPG) (Step 1); Mixing the first mixture with a surfactant to form a second mixture (step 2); And a step (3) of preparing an eco-friendly adhesive composition by stirring the second mixture. This is because it has excellent adhesive strength, does not cause yellowing, and quickly cures And does not contain heavy metals or volatile organic compounds (VOC).

On the other hand, in the present invention, hydrophilic polyols such as PEG used for imparting moisture permeability to a hot-melt adhesive are poor in surface properties due to swelling due to hydrophilization of the adhesive, lowering of water-resistant adhesive strength, And a coating material using the reactive polyurethane hotmelt adhesive for moisture permeable textile material coating was developed.

Korean Patent Laid-Open Publication No. 10-2008-0088628 (published date: October 02, 2008) Korean Patent Publication No. 10-2010-0041692 (published on Apr. 22, 2010) Korean Patent Laid-Open Publication No. 10-2011-0022764 (public date: 2011. 03. 08)

It is an object of the present invention to provide a water-repellent and non-swelling property by mixing a specific hydrophilic polyether polyol and a polyester polyol to impart hydrophilicity and non-swelling characteristics, It contains a reactive silicone oil to strengthen the non-expansion property, a moisture absorber for adjustment of the reaction rate, and an adhesive reinforcement to improve the adhesive strength, thereby preventing the drop of the adhesive strength, A reactive polyurethane hot melt adhesive for coating a textile material having good non-swelling properties and a method for producing a coated fabric using the same.

The reactive polyurethane hot-melt adhesive according to the present invention comprises (a) 10 to 40% by weight of a hydrophilic polyether polyol having a number average molecular weight of 1,000 to 2,000 and a hydroxyl value of 56 to 110 mg KOH / g; (b) 0 to 25% by weight of a hydrophobic polyether polyol having a number average molecular weight of 1,000 to 2,000 and a hydroxyl value of 56 to 110 mg KOH / g; (c) 1 to 3% by weight of a reactive silicone oil having a number average molecular weight of 3,000 to 5,000; (d) at least one diol selected from 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, ethylene glycol, and hexanediol is reacted with adipic acid or isophthalic acid 30 to 60% by weight of a polyester polyol prepared by blending a polyester polyol having a number average molecular weight of 2,000 to 4,000 and a hydroxyl value of 25 to 55 mgKOH / g with polycaprolactone (PCL) at a weight ratio of 1: 0.8 to 1.2; (e) 15 to 30% by weight of a diisocyanate; (f) 0.5-1 wt% of a hygroscopic agent; (g) 1 to 5% by weight of an adhesive reinforcing agent; (h) 0.1 wt% of the catalyst, the viscosity is 4,000-12,000 cps / 100 deg. C, and the NCO content is 1.8-3.0 wt%.

According to a preferred embodiment of the present invention, the hydrophilic polyether polyol (a) is an ethylene oxide / tetrahydrofuran block copolymer (EO / THF) in which the molar ratio of ethylene oxide / tetrahydrofuran (EO / THF) / THF block copolymer, and the hydrophobic polyether polyol (b) is any one selected from the group consisting of polypropylene glycol, polybutylene glycol and polytetramethylene glycol.

Also, the moisture absorbent (f) uses para-toluenesulfonyl isocyanate for adjusting the reaction rate, and the adhesion enhancer (g) is an adhesive strength by use of a hydrophilic polyether polyol and a reactive silicone oil Xylene-glycol resin is used to reinforce.

The reactive polyurethane hot melt adhesive is melted at a temperature of 80 to 120 ° C and applied to the fiber fabric in an amount of 5 to 50 g / m 2, At a temperature of 50 ° C and a relative humidity of 70 to 100% for 12 to 48 hours, and the coated fabric has a moisture permeability of 3,000 to 5,000 g / m 2day and a peel strength of 18 to 27 kgf / 2 cm .

The reactive polyurethane hot melt adhesive of the present invention can be produced by mixing a hydrophilic polyether polyol prepared by using an ethylene oxide / tetrahydrofuran block copolymer (PO / THF block copolymer) having a number average molecular weight of 1,000 to 2,000 and a polyester polyol, And non-swelling properties, thereby improving the surface properties and the water-resistant adhesive strength. To this end, a reactive silicone oil for enhancing non-expansion characteristics and a moisture absorber for adjusting the reaction rate and an adhesive reinforcement And the like, it has an effect that moisture permeability and adhesive strength are excellent and storage and processing stability are improved.

The reactive polyurethane hot melt adhesive of the present invention is an environmentally friendly polyurethane adhesive of 100% solids which does not use a solvent and is adhered to a fiber material by thermal melting. Therefore, adhesive strength and peel strength It is possible to produce a coated fabric having excellent physical properties and soft touch.

Hereinafter, a reactive polyurethane hot-melt adhesive having a non-expanding property according to the present invention and a method of producing a coated fabric using the same will be described in detail. However, the present invention is not limited thereto, It should be understood, however, that the technical spirit and scope of the present invention are not limited by the foregoing description.

The reactive polyurethane hot-melt adhesive according to the present invention comprises (a) 10 to 40% by weight of a hydrophilic polyether polyol having a number average molecular weight of 1,000 to 2,000 and a hydroxyl value of 56 to 110 mg KOH / g; (b) 0 to 25% by weight of a hydrophobic polyether polyol having a number average molecular weight of 1,000 to 2,000 and a hydroxyl value of 56 to 110 mg KOH / g; (c) 1 to 3% by weight of a reactive silicone oil having a number average molecular weight of 3,000 to 5,000; (d) at least one diol selected from 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, ethylene glycol, and hexanediol is reacted with adipic acid or isophthalic acid 30 to 60% by weight of a polyester polyol prepared by blending a polyester polyol having a number average molecular weight of 2,000 to 4,000 and a hydroxyl value of 25 to 55 mgKOH / g with polycaprolactone (PCL) at a weight ratio of 1: 0.8 to 1.2; (e) 15 to 30% by weight of a diisocyanate; (f) 0.5-1 wt% of a hygroscopic agent; (g) 1 to 5% by weight of an adhesive reinforcing agent; (h) 0.1% by weight of catalyst, and has a viscosity ranging from 4,000 to 12,000 cps / 100 ° C and an NCO content of 1.8 to 3.0% by weight.

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. As a result, the polyurethane resin is characterized by its high film strength and adhesive strength, so that it is possible to produce a thin coating film, and the elasticity of the coating film is abundant, so that the soft feeling can be made and the film can be made into a porous film film, But also has excellent cold resistance, and since it is processed without using a plasticizer, there is little workability problem caused by the plasticizer.

Polyol is an active hydrogen compound used in the production of polyurethane by reacting with isocyanate and having two or more active hydrogen groups such as hydroxyl group, carboxyl group and amine group in the molecule. Ethylene glycol, glycerine, butanediol, trimethylol propane, and low molecular weight polyols are used as chain extenders or crosslinking agents, and the average High molecular weight polyols with molecular weights up to 8,000 are actually used for polyurethane production.

As described above, 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 polyurethane. For example, a polyurethane using a polyester polyol has a higher tensile strength, hardness and elongation than the polyurethane using a polyether polyol, has excellent flame retardancy, is excellent in chemical resistance and chemical resistance, and is resistant to oxidation. In addition, it has a good adhesion to polyester fabric, but has a property of hydrolyzing, unlike polyether polyol, and has a weak water resistance. However, polyurethane using polyether polyol has excellent elasticity and shows excellent durability against acid and alkali, so it can be used under high temperature and high humidity environment.

On the other hand, the reactive polyurethane hot-melt adhesive of the present invention is basically made of a polyurethane prepolymer composed of a hydrophilic polyether polyol (a), a reactive silicone oil (c) and a diisocyanate (e) A polyester polyol (d) and a hydrophobic polyether polyol (b).

The polyurethane prepolymer is produced by reacting a hydrophilic polyether polyol (a) and a reactive silicone oil (c) for imparting non-expansion characteristics with a diisocyanate (e) in a primary reaction. As the hydrophilic polyether polyol (EO / THF block copolymer) and polyethylene glycol (PEG) can be used in the present invention.

The ethylene oxide / tetrahydrofuran block copolymer (EO / THF block copolymer) may be any of copolymers having molar ratios of EO / THF of 3/7, 5/5 and 7/3. In the present invention, it has been confirmed that the hot-melt adhesive manufactured at a molar ratio of 5/5 has more stable moisture permeability and non-expansion property. The number average molecular weight of the EO / THF block copolymer may range from 1,000 to 4,000. Preferably, the EO / THF block copolymer has a number average molecular weight of 1,000 to 2,000 and a hydroxyl value of 56 to 110 mgKOH / g. And process stability.

In order to improve the moisture permeability of the hot melt according to the present invention, polyethylene glycol (PEG) may be used in an amount of about 0 to 10% by weight based on the weight of the polyol. In order to minimize physical properties and swelling properties, Should be used. When PEG having higher molecular weight is used, moisture permeability can be improved but swelling is increased, and when lower molecular weight PEG is used, the moisture permeability is lowered.

The hydrophilic polyether polyol (a) is used in an amount ranging from 10 to 40% by weight based on the total amount of the hot melt adhesive. When the proportion of the hydrophilic polyether polyol exceeds 40% by weight, the strength and adhesion of the reactive hot melt adhesive are inferior, If it is lower than 10% by weight, the moisture permeability is low. The hydrophilic polyether polyol is sufficiently thermally dried before the reaction to minimize moisture in the polyol and is used in the reaction.

In addition, in the present invention, the hydrophobic polyether polyol (b) optionally used for the mechanical strength and the tactile optimization of the hot-melt adhesive may be any one selected from the group consisting of polypropylene glycol, polybutylene glycol and polytetramethylene glycol Among them, polypropylene glycol having a number average molecular weight of 1,000 to 2,000 and a hydroxyl value of 56 to 110 mg KOH / g is most preferable. The hydrophobic polyether polyol can be applied at a weight ratio of 25% or less based on the total weight of the hot-melt adhesive.

In the present invention, the reactive silicone oil (c) used for maximizing the non-swelling property is a silicone oil having a number average molecular weight of 1,000 to 5,000 and a reactive silicone oil of a bi- In order to maximize the non-expansion characteristics, it is preferable to apply a bi-terminal type reactive silicone oil having a number average molecular weight of 3,000 to 5,000 in an amount of 1 to 5% based on the total amount of the adhesive in the first reaction, , And more preferably 1 to 3 wt%. When the non-reactive silicone oil is applied, the non-expanding property is excellently exhibited, but the adhesive force is remarkably lowered. This phenomenon is also observed when the reactive silicone oil is applied at 5% or more.

As the polyol for producing the polyurethane adhesive of the present invention, a mixture of a polyether polyol having good flowability and a polyester polyol having excellent adhesive strength was used in consideration of characteristics such as viscosity and adhesive force of a reactive polyurethane hot melt adhesive as a target product. At this time, it is preferable that the polyol is mixed with 10 to 40% by weight of the polyether polyol and 30 to 60% by weight of the polyester polyol based on the total weight of the hot-melt adhesive to exhibit excellent flowability and strong adhesive force. The viscosity, the feel, and the adhesive strength of the resin itself are reduced.

The polyester polyol (d) is a polyester derived from a dicarboxylic acid and a diol and / or derived from a hydroxycarboxylic acid or a corresponding lactone or lactide, such as, for example, polyneopentyl adipate, Dimethylol-1,3-propanediol, 1,4-butanediol, ethylene glycol and hexanediol, and adipic acid or isophthalic acid are reacted singly or simultaneously to give a number average molecular weight of 2,000 to 4,000 Amorphous or crystalline polyester polyol and polycaprolactone (PCL) prepared by a conventional method having a hydroxyl value of 25 to 55 mg KOH / g in a weight ratio of 1: 0.8 to 1.2.

The polyester polyol (d) prepared as described above is preferably 60 to 80% by weight relative to the total amount of the polyol. When the amount is out of the range, viscosity, tactile sensation, and adhesive strength of the resin deteriorate. The ratio of the total polyol to the final polyurethane hotmelt adhesive is preferably 70 to 85% by weight. When the proportion of the polyol is less than 70% by weight, the tactile feeling and the adhesive strength are lowered. When the content is more than 85% by weight, have.

In the present invention, the diisocyanate (e) for the reaction of the hot-melt resin may be an aromatic isocyanate compound used in the production of conventional polyurethanes. Preferably, a compound selected from the group consisting of diphenylmethane diisocyanate (MDI), polycarbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate (TDI), and a mixture of at least one thereof may be used. It is preferable to mix MDI with modified MDI in a molar ratio of 10 to 20%.

The reactive hot-melt adhesive of the present invention can be obtained by simple mixing and reacting the hydrophilic (a), hydrophobic polyether polyol (b) and reactive silicone oil (c) used in the reaction with diisocyanate (e) The hot melt adhesive may be prepared by mixing the hydrophilic polyol (a) and the reactive silicone oil (c) with the diisocyanate (e) and then reacting the hydrophobic polyether polyol (b) It is confirmed that the two-step reaction is advantageous in order to maximize the swelling characteristics of the hot-melt adhesive under the same conditions.

The reactive hot melt adhesive prepared by the first reaction using the diisocyanate (e) at a temperature of 80 to 90 ° C for 1 to 2 hours has an NCO content of 2.5 to 3.5 wt% and a viscosity of 1,000 to 10,000 cps / Range. When the remaining hydrophilic (a) or hydrophobic polyether polyol (b) is added after the first reaction and subjected to a second reaction for 2 hours under the same conditions, the viscosity is 4,000 to 12,000 cps / 100 ° C and the NCO content is 1.8 to 3.0% .

When the NCO content of the polyurethane hot melt adhesive thus synthesized is higher than 3.0 wt%, the mechanical properties of the final coated product are improved, but the feeling of touch is generally lowered. If the viscosity is higher than the above range, the tactile sensation is improved to a certain level, but the workability is lowered. If the viscosity is lower than this range, the penetration of the adhesive into the fabric increases, and the feeling of the coated fabric becomes hard.

On the other hand, the hygroscopicity of the hydrophilic polymer deteriorates the reactivity upon reaction of the hot-melt adhesive, absorbs moisture and absorbs moisture during storage or processing due to the nature of the reactive hot-melt adhesive, Respectively. Accordingly, after the reaction, the storage stability and the hygroscopicity at the initial stage of the reaction are minimized, and the moisture absorbent (f) after the reaction is used to adjust the reaction rate and open time. As the moisture absorbent (f), a generally used gaseous moisture absorber or a reactive moisture absorber may be used. In the present invention, in order to minimize side reactions and to optimize adhesion and moisture permeability, a p-toluenesulfonyl isocyanate Was used in a range of 0.5 to 1% by weight based on the total weight of the composition.

Also, in the present invention, xylene-glycol resin is applied in an amount of 1 to 5 wt% based on the total weight of the adhesive reinforcing agent (g) for reinforcing the adhesive strength which is lowered due to the use of the hydrophilic polyether polymer and the reactive silicone oil.

The reactive polyurethane hot melt adhesive is melted at a temperature of 80 to 120 DEG C and applied to the fiber fabric in an amount of 5 to 50 g / m < 2 >, followed by heating at a temperature of 30 At 50 ° C and a relative humidity of 70-100% for 12-48 hours.

The hot-melt adhesive is melted using a melting facility of 80 to 120 ° C and then coated on the moisture-permeable and waterproof functional film using a doctor blade, a gravure roll or a full roll at a viscosity of 5,000 to 20,000 cps / 100 ° C, And the application amount of the adhesive to be transferred is appropriately from 5 to 50 g / m < 2 >. If the amount of the hot-melt adhesive applied is less than 5 g / m 2, the adhesive strength is lowered. If the amount of the hot-melt adhesive is more than 50 g / m 2, the feel of the product is lowered.

The reactive polyurethane hot melt adhesive of the present invention exhibits stronger adhesion and mechanical properties than conventional hot melt adhesives by reacting with an isocyanate group at the end of a polyurethane adhesive, a fabric, a functional film, and moisture contained in the air. Therefore, after performing the fiber bonding or laminating process for fiber materials, the optimum physical properties are exhibited after aging for 12 hours or more at a temperature of 30 to 50 ° C. and a relative humidity of 70% or more.

As described above, the coated fabric to which the reactive hot-melt adhesive of the present invention is applied has a water vapor permeability of 3,000 to 5,000 g / m 2day (ASTM E96 BW method (32 ° C × 50% RH)), (non-swelling) property, and the coated fiber material produced therefrom has a good tactile feel as well as a peel strength of 18 to 27 kgf / 2 cm.

Hereinafter, a reactive polyurethane hot melt adhesive according to the present invention and a coated fabric prepared using the same will be described in detail with reference to the following examples. Explain.

[Example 1] - [Example 3], [Comparative Example 1] - [Comparative Example 3]

860 g of EO / THF copolymer, 18 g of bi-termial type reactive silicone oil and 3 g of antioxidant were added to the 3-liter three-necked reflux reactor under nitrogen atmosphere and sufficiently stirred. 43 g of MDI, 82 g of denatured MDI, 3 g of moisture-curing catalyst (DMDEE) and 12 g of modaflow were added and reacted at 80 to 100 ° C for 2 hours until the NCO value reached 2.7 to 3.5% by weight. After stabilizing the NCO value, 729 g of polycaprolactone, 582 g of polyester polyol and 30 g of xylene-glycol resin were added and reacted at a temperature of 80 to 100 ° C for 2 hours. Then, the reaction was conducted under vacuum for 1 hour to remove unreacted isocyanate . When the NCO value is 2.2 to 3.0 wt%, the reaction is terminated and 16 g of the moisture absorber and 3 g of phthalic anhydride are added and stirred well. Synthesis of a reactive polyurethane hot melt adhesive having different components in different compositions was carried out in the composition shown in Table 1 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 EO / THF copolymer 860 650 1,060 0 860 860 PEG 0 0 270 500 0 0 Reactive silicone 18 14 28 21 0 18 PCL 729 729 729 729 729 729 Polyester polyol 582 582 582 582 582 582 PPG 0 300 0 200 0 0 Isocyanate 519 640 699 738 516 519 Absorbent 16 17 10 16 16 0 Adhesive reinforcement 30 32 37 30 30 0

[Experimental Example]

The adhesive strength, mechanical strength, moisture permeability, non-swelling properties, and tactile properties of the hot-melt adhesives prepared according to Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 2 Respectively.

- Adhesive strength test

A PTFE film (30 탆, 24 g / m 2) and Poly Dewspo 50D were used as the test pieces for the peel strength test of the hot-melt adhesive prepared in Examples 1 to 3 and Comparative Examples 1 to 3. The hot-melt adhesive was melted at a temperature of 100 ° C., and then transferred onto the surface of the PTFE film using a roll and a doctor blade so that the application amount was 30 g / m 2. Then, the rubber melt and the dope roll were used to press the dewspo fabric. . At this time, 5 specimens were used for the same test, and a universal tensile tester was used for the test. The breaking load of the test machine and the test specimen was set within 5 ~ 85% of the capacity. The adhesion test was carried out 5 times after aging at 40 ° C and 70% relative humidity for 12 hours.

- Mechanical strength

In order to measure the mechanical strength of the hot-melt adhesive prepared in Examples 1 to 3 and Comparative Examples 1 to 3, the hot-melt adhesive was melted at a temperature of 100 ° C., and then was completely coated on the RP to a thickness of 30 μm using a roll After aging for 12 hours at a temperature of 40 ° C and a relative humidity of 70%, tensile strength and elongation were measured using a universal tensile tester.

- Water vapor permeability

Measured by ASTM E96 BW inverted water method

- non swelling characteristics

The hot-melt adhesive prepared in Examples 1 to 3 and Comparative Examples 1 to 3 and a PTFE film Dewspo D50 fabric were assembled to measure the tactile sensation of ten experts.

-touch

The hot-melt adhesive prepared in Examples 1 to 3 and Comparative Examples 1 to 3 and a PTFE film Dewspo D50 fabric were assembled to measure the tactile sensation of ten experts.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Peel strength
{kgf / 2 cm} 24 27 21 18 25 19 Moisture permeability
{g / m2day} 3,500 2,800 5,000 4,000 3,600 3,500 Non-Swelling Characteristics ◎ ◎ ○ × ○ ◎ The tensile strength
{Kgf / cm2} 180 190 150 210 170 180 Shinto {%} 650 600 450 350 600 700 touch ◎ ◎ ◎ ○ ○ ◎

* Non-swelling characteristics and touch: Excellent ◎> ∘> △> × Poor

As shown in Table 2, when the experimental results of Examples 1 to 3 and Comparative Examples 1 to 3 are compared, in the case of Example 1, the moisture permeability of about 3,500 g / m 2day, stable non-swelling characteristics, Tensile strength. When the ratio of EO / THF copolymer was decreased, the moisture permeability was reduced as in Example 2, but mechanical properties improved in peel strength and tensile strength were confirmed. In addition, when the EO / THF copolymer and PEG were blended with 50 wt% of the total polyol, the highest moisture permeability was obtained. The higher the hydrophilic polyether polyol ratio, the higher the moisture permeability but the low swelling property and the relatively low peel strength .

In the case of Comparative Example 1 for Example 1, the non-swelling property of the silicone additive was found to be different from that in the case of Comparative Example 2, and in Comparative Example 3 for Example 1 It is possible to confirm the difference in peel strength due to the introduction of the adhesive reinforcing agent. When the results of Examples 1 and 2 are compared, it can be confirmed that the mechanical strength and the adhesive strength of the resin vary depending on the ratio of the hydrophilic polyether polyol, polycaprolactone and polyester polyol.

From the above-mentioned experimental results, Example 1 exhibited excellent physical properties in terms of moisture permeability, non-swelling property, adhesive strength, viscosity, and tactile surface even when the entire surface was coated.

Accordingly, the reactive polyurethane hotmelt adhesive of the present invention can be variously substituted, modified and changed within the scope of the technical idea of the present invention, and is advantageous in workability. Thus, the surface of various textile materials, , And can be used in various applications and forms such as being coated on a building material or bonded in a film form.

Claims (7)

(a) an ethylene oxide / tetrahydrofuran block copolymer having a number average molecular weight of 1,000 to 2,000 and a hydroxyl value of 56 to 110 mg KOH / g, the molar ratio of ethylene oxide / tetrahydrofuran (EO / THF) being 5/5 10 to 40% by weight of a hydrophilic polyether polyol composed of an EO / THF block copolymer;
(b) a hydrophobic polyether polyol composed of any one selected from the group consisting of polypropylene glycol having a number average molecular weight of 1,000 to 2,000 and hydroxyl group of 56 to 110 mg KOH / g, polybutylene glycol and polytetramethylene glycol, 25% by weight;
(c) 1 to 3% by weight of a reactive silicone oil having a number average molecular weight of 3,000 to 5,000;
(d) at least one diol selected from 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, ethylene glycol, and hexanediol is reacted with adipic acid or isophthalic acid 30 to 60% by weight of a polyester polyol prepared by blending a polyester polyol having a number average molecular weight of 2,000 to 4,000 and a hydroxyl value of 25 to 55 mgKOH / g with polycaprolactone (PCL) at a weight ratio of 1: 0.8 to 1.2;
(e) 15 to 30% by weight of a diisocyanate;
(f) 0.5-1 wt% of a hygroscopic agent;
(g) 1 to 5% by weight of an adhesive reinforcing agent;
(h) 0.1 wt% catalyst;
Of 4,000 to 12,000 cps / 100 ° C and an NCO content of 1.8 to 3.0% by weight based on the total amount of the reactive polyurethane hot-melt adhesive. delete delete The method according to claim 1,
Wherein the moisture absorbent (f) is p-toluenesulfonyl isocyanate for adjusting the reaction rate. The reactive polyurethane hot melt adhesive according to claim 1, wherein the moisture absorbent (f) is p-toluenesulfonyl isocyanate. The method according to claim 1,
Wherein the adhesive reinforcement agent (g) uses xylene-glycol resin to reinforce the adhesive force by use of the hydrophilic polyether polyol and the reactive silicone oil. The reactive polyurethane hot melt adhesive according to any one of claims 1 to 5 is melted at a temperature of 80 to 120 ° C and applied to the fiber fabric in an amount of 5 to 50 g / At a temperature of 50 DEG C and a relative humidity of 70 to 100% for 12 to 48 hours. The method according to claim 6,
Wherein the coated fabric has a moisture permeability of 3,000 to 5,000 g / m 2day and a peel strength of 18 to 27 kgf / 2 cm.