KR101204905B1 - Manufacturing process of flocking artificial leather using binder of slovent free urethane and product manufactured thereby - Google Patents

Abstract

PURPOSE: A method for fabricating flocking artificial leather using a solvent-free urethane binder is provided to plant ultra-fine short staples using the solvent-free urethane binder and to improve texture and flame retardancy. CONSTITUTION: A method for fabricating flocking artificial leather using a solvent-free urethane binder comprises: a step of reaction of isocyanate to a polyol mixture containing crystalline polyol, non-crystalline polyol, flame retardant polyol, and chain extenders and synthesizing urethane prepolymer(ingredient A) containing hydroxyl groups at both ends at 60 Deg. C.; a step of fusing the urethane prepolymer ingredient at less than 60 Deg. C.; a step of putting predetermined amount of fused urethane prepolymer(ingredient A), isocyanate-based compounds(ingredient B), and additives(ingredient C) containing crosslinking curing catalyst and surfactant into a high speed molding device through a separate line; a step of stirring and mixing at high speed; a step of discharging the reaction mixture solution onto a water dispersion urethane-microfoaming fiber substrate; a step of forming a binder layer; a step of flocking fiber piles to the binder layer; a step of crosslinking and curing the same at 80-150 Deg. C.; and a step of brushing the same and post-curing at 30-80 Deg. C. [Reference numerals] (AA) Solvent free urethane adhesive; (BB) Fiber base(filament high density ultrafine fiber)

Description

Manufacture method of flocking artificial leather using solvent-free urethane type binder and processed product using same {manufacturing process of flocking artifical leather USING BINDER OF SLOVENT FREE URETHANE AND PRODUCT MANUFACTURED THEREBY}

The present invention relates to a method of manufacturing artificial artificial leather using a solvent-free urethane-type binder and processed products using the same. More specifically, it does not contain organic solvents harmful to the human body, so it is environmentally friendly and structurally strong in cohesive strength, peel strength, tensile strength, heat resistance, Flocking process using Solvent free urethane binder resin with excellent elasticity and hydrolysis resistance not only improves the hair density, the uprightness of the hair, the smoothness of the hair, the wear resistance, the touch, etc., but also the molding processability, flame retardancy, The present invention relates to a method for manufacturing high quality environmentally friendly flocked artificial leather with improved flexibility and functional post-processing, post-dyeing and production efficiency, and processed products using the same.

In general, the flocking process uniformly applies a binder onto a fabric base on a woven or nonwoven fabric, and electrically coats the fiber pile cut to a predetermined length using a constant voltage on the upper surface thereof to possess an appearance and texture similar to that of natural leather. Refers to the manufacture of artificial leather.

In the conventional flocking process, polymer resins containing organic solvents such as dimethylformamide (DMF) and methyl ethyl ketone (MEK) have been used as binders, but these organic solvents are toxic substances harmful to humans. Recently, an artificial leather manufacturing method using an aqueous resin binder has been developed.

As an example of a flocking product and a leather-type sheet using an aqueous resin binder as described above, WO 2004/081058 discloses a method of processing artificial leather using a flocking binder containing a vinyl emulsion composition. However, these aqueous resin binders have poor water resistance, peel strength, mechanical properties and durability due to difficulty in controlling molecular weight, limited selection of synthetic raw materials, and fundamental limitations in the synthesis process. There was a problem that there is a limit to the use deployment.

In addition, Japanese Patent Laid-Open Publication Nos. 2002-249534, 2003-049147, 2004-115705, and Korean Patent 2006-0127979, WO 2005/083173, and the like, use a solvent-free reactive urethane resin, in which organic solvents are excluded. A method for producing a polyurethane foam sheet, a leather-like sheet or a binder through has been proposed.

The reactive hot-melt urethanes are mostly solid at room temperature, melt when heated, and become liquid, and cohesive force is expressed again by cooling, and physical properties due to crosslinking reactions due to reaction with isocyanate groups and moisture (water). In addition to having a 'moisture curing property', which has recently been attracting attention in various fields as a manufacturing method of an environmentally friendly resin excluding an organic solvent.

However, in the case of using a moisture-curable urethane based on an isocyanate group-end prepolymer as described above, even if the process conditions such as temperature and humidity are slightly changed, the peel strength and other physical properties are severely changed. It is difficult to produce reproducible products because of the difference, and the melting temperature of the component A urethane prepolymer is usually 100 ° C. or more, which is very high, and it takes a long time to melt, and the temperature and viscosity of the reaction solution are relatively high. The gelation time was short and the flowability was also lowered, resulting in poor production stability and uniformity of the product.

Therefore, in order to solve such a problem, WO 2001/96435 and Korean Patent Registration 10-0573044 describe a method of introducing a liquid prepolymer, which is because the gelation time of the reaction solution of the urethane prepolymer and the curing agent is extended. It has the effect of good flow and good work stability.

However, these liquid prepolymers have low production efficiency as the aging time, which is a post-curing process, is usually longer than 3 to 5 days, and synthesized and processed around raw materials that are liquid at room temperature to control the state at room temperature to liquid phase. Therefore, even after a certain period of hardening, the solidification rate is slow and structurally weak cohesion acts as a deterioration factor of physical properties, and thus it cannot satisfy the physical properties such as mechanical properties, peel strength, heat resistance, and hydrolysis resistance required by the leather type sheet. No results were obtained.

In addition, Korean Patent Nos. 10-0581330 and 10-0591638 disclose a method of manufacturing artificial leather using a solvent-free polyurethane foam, which is a foam head with a liquid ratio determined by urethane raw material according to the use of a product by a precision pump. The artificial leather is manufactured by discharging immediately after mixing through it, and the composition and appearance of the surface part during the manufacturing of artificial leather due to uneven foaming due to its properties are separated by peeling the skin rule coated with a solvent-type urethane resin on the release paper carved into the pattern. The fiber base part of artificial leather is simply joined by discharging these two with 100% solvent-free binder by using impregnated nonwoven fabric and knitted fabric using existing solvent.

Therefore, the skin and impregnated fiber base of the artificial leather is not an environmentally friendly artificial leather, the appearance of the chinchilla-like (chinchilla-like apperance) and natural suede, the fiber is finely expressed to the skin portion using the release paper as a surface portion There was little to express the natural nubuck leather with chalk marks and hand effects due to its texture and suede effect.

On the other hand, artificial leather products manufactured for flooring, automobiles, and interiors through flocking processes are required to be flame retardant due to the fire risks in accordance with the law. Incorporation of flame retardants has been used.

However, this method does not show uniform flame retardant effect due to poor compatibility between the flame retardant and the polymer resin, and the flame retardant is bleed out to the surface of the molded article to reduce the flame retardant effect, and also generates harmful gas upon incineration. Since the flame retardant compound itself is toxic, there is a problem in that it is not preferable in terms of environmental pollution.

As a result of the above-mentioned flocked artificial leather manufacturing technology, the meltability can be melted even at a relatively low temperature (below 60 ° C) in order to improve the mechanical properties, abrasion resistance, molding processability, production efficiency and product uniformity of the product. It is desirable to utilize a solvent-free urethane adhesive having high strength and 100% solids with adequately controlled crystallinity, rigidity and cohesion so as to improve crosslinking curing and solidification rate while maintaining an appropriate viscosity at a constant temperature.

In addition, the conventional isocyanate group terminal prepolymer has a high risk of deformation or deterioration due to reaction with moisture, and thus requires a special packaging method to secure storage stability, and a separate device for securing stability even in the process of melting the prepolymer at a high temperature is provided. As necessary, it is therefore desirable to utilize hydroxyl end prepolymer materials that are relatively stable to ambient moisture and atmosphere for efficient molding and reaction processes.

However, the research on the method for producing a flocked artificial leather that can satisfy the above conditions is still insufficient, and the present inventors have a high quality environment by utilizing binders and resins that are different from the existing solvent-free urethane type system. It has come to the completion of the method of manufacturing friendly flocking artificial leather.

Therefore, the present invention is configured to solve the above problems, conventional flocking process system utilizing a high strength solvent-free urethane binder (resin free urethane) binder and resin excellent in tensile properties, peel strength, heat resistance, hydrolysis resistance, etc. Compared to density, abrasion resistance, touch, flame retardancy, etc., the gelation time is long and crosslinked while showing the proper melting temperature and viscosity. Its purpose is to provide an environmentally friendly method for producing flocked artificial leather with improved curing processability and production efficiency due to its high curing rate and fastening speed.

According to an aspect of the present invention,

(a) a urethane prepolymer having a hydroxyl group having a melt viscosity of 1,000 to 20,000 cps at both ends at 60 ° C. by reacting isocyanate with a polyol mixture composed of crystalline polyol, amorphous polyol, flame retardant polyol, and chain extender [component A] Synthesizing;

(b) melting the urethane prepolymer component at 60 ° C. or below:

(c) A fixed amount of molten urethane prepolymer [component A], an isocyanate compound [component B], and an additive [component C] containing a crosslinking curing catalyst and a foaming agent in a fixed amount in a high-speed reaction molding machine through separate lines. And then stirring and mixing at high speed;

(d) discharging the reaction mixture onto a fibrous substrate finely dispersed with water-dispersed urethane therein, and then performing a knife or comb coating to form a binder layer:

(e) Flocking the fiber pile on the binder layer, crosslinking, curing and brushing under a temperature condition of 80 ℃ to 150 ℃, then lowering to a temperature of 30 to 80 ℃ and post-curing using a solvent-free urethane binder To provide a method for manufacturing artificial leather.

In addition, the present invention in order to achieve another object, by the above-described manufacturing method to the natural leather texture and appearance, moisture permeability, water repellency and environmentally friendly functional flocking artificial leather shoes, clothing, furniture, automobile An object of the present invention is to provide a flocked artificial leather processed product, which is processed to be used as a skin material such as interior materials.

As described above, the method for producing a flocked artificial leather using the solvent-free urethane-type binder of the present invention and processed products using the same are composed of a surface part by high-density seeding type ultrafine short fibers into a fiber base with a 100% solid-free solvent-free binder. The micro foaming of water-dispersed urethane with Foaming Mixer is used to form pores inside, which improves density, touch and flame retardancy compared to conventional flocking process systems. It has high cross-linking and curing ability, and has a high rate of solidification during cooling, so it can provide high quality eco-friendly flocking products with improved molding processability and production efficiency.It can be widely used for furniture interiors and automobiles that require high durability. Has the effect of

1 is a photograph showing a flocking artificial leather produced by the manufacturing method of the present invention.

Hereinafter, a method of manufacturing the flocked artificial leather of the present invention will be described in more detail.

In the present invention, by using the flocking processing process of the ultra-fine split fibers to form a surface portion of natural leather silver noodles by high-density seeding type ultra-fine short fibers to 100% solids solvent-free binder in the fiber base material, the fiber base is natural It is impregnated with fine foaming of water-dispersed urethane with Foaming Mixer in the textile fabric completed by thermal and physical division process and high shrinkage expression process with silver layer surface and intermediate fiber of leather.

The 100% solvent-free binder used in the present invention has no change in solid content after application and has a smooth, high-molecular structure, which is a micro-microfiber N / P composite conjugate yarn that was impossible to apply due to adhesive property problems with conventional flocking binders. N / P composite yarn of 0.1 denier micro-microfiber is divided into 70% to 85% PET and 15% to 30% nylon and 15% to 30% nylon. By expressing the pitch and feel of the surface of artificial leather, it can express the outstanding performance, skin-friendly effect, and the appearance of elegant melange color.

In addition, the aqueous polyurethane impregnation process (Foaming Mixer) in the fiber substrate of the present invention is a process of imparting elasticity and form stability by forming micropores in the fiber substrate with aqueous urethane, it is stable at room temperature and has excellent thermal and coagulation properties, It is a process of forming an internal structure such as collagen of natural leather by filling a nonwoven fabric surface uniformly without ubiquitous phenomenon to form a porous layer.

Such a water-based urethane mixing process is possible by utilizing a steaming process, which impregnates a fiber base such as a nonwoven fabric in an aqueous urethane mixture, and adjusts the wet pick-up to an appropriate amount by mangle. After squeezing, the temperature of steam is raised above the temperature of the aqueous urethane resin heat-gelling temperature, and finely foamed in saturated water vapor for a suitable time, heat and solidify, and then dry.

The temperature and solidification temperature of the water-based urethane resin is generally suitable 40 ~ 100 ℃, which is a problem such as the stability of the resin itself, especially in the summer, such as agglomeration or gelling in the summer, 100 ℃ or more In this case, the efficiency of coagulation decreases, so that resin is not uniformly filled in the fiber base, and there is a possibility of surface unevenness. In addition, when high temperature and high pressure steam must be used, productivity and economic considerations are considered. Inappropriate.

The manufacturing method of the flocked artificial leather is developed by the precise short cut process in the case of the microfibers implanted in the surface part, and it is not possible to recycle it with the composite spinning structure, and tow the unstressed yarn which was developed outside the original use. Therefore, the eco-friendly meaning of recycling is strong. In addition, the artificial leather manufactured through the flocking process is a high-durability, environmentally friendly functional artificial leather possessing texture, appearance, moisture permeability, water repellency, and the like close to natural leather, such as shoes, clothing, furniture, and automotive interior materials. It can be used as.

In addition, the aesthetic, physical properties, and aesthetics required by the market through a series of processes such as selection of application yarn, high shrinkage processing of ultra-fine fabrics, water impregnation / tannery processing, high fastness dyeing / processing, eco-friendly / functional post-treatment, and flame retardant processing It can be selectively responded to functional needs and manufactured in combination in the form of environmentally friendly functional micro artificial leather, which can be expanded to various end products of natural leather.

1 is a photograph showing a flocked artificial leather produced by the manufacturing method of the present invention, as shown therein largely composed of a fiber base layer (1), a solvent-free urethane binder layer (2), a pile fiber layer (3) do.

First, the solvent-free urethane-type binder layer 2 is a hydroxyl group-terminated urethane prepolymer [component A] and an additive [component C] including a isocyanate compound [component B] and a catalyst and foam stabilizer as a crosslinking agent capable of reacting with a hydroxyl group. The reaction mixture is characterized in that.

The hydroxyl terminal prepolymer as the [component A] is a reaction mixture of a polyol component such as a polyol having a crystalline structure, an amorphous amorphous polyol, a flame retardant polyol, a chain extender, and an isocyanate component, and both ends of which are hydroxyl groups.

In addition, the isocyanate compound as the [component B] is a modified aromatic polyisocyanate compound, a modified aliphatic polyisocyanate compound, a prepolymer containing an isocyanate group at both terminals, or a mixture thereof, at room temperature in a low viscosity liquid state.

This hydroxyl group terminated urethane prepolymer [component A] is melted at a temperature range of 60 ° C. or lower, and then an isocyanate compound [component B] capable of reacting with the hydroxyl group, an additive containing a crosslinking curing catalyst and a foaming agent [ Component C] was quantitatively charged into the high-speed reaction molding machine, and then the mechanical reaction mixture obtained by high-speed stirring was applied onto the fibrous base material 1 finely foamed with the water-dispersed urethane to form a binder layer 2 to form a flocking sheet. To prepare.

Subsequently, the fiber pile 3 is laminated on the binder layer 2 and heated under a temperature condition of 80 to 150 ° C. to crosslink and cure the binder layer 2 of the flocking sheet, and then brushed, and the heating temperature is 30 to It is completed by lowering to 80 ° C and aging for an appropriate time, followed by curing.

Referring to the characteristics of each raw material used in the present invention in detail.

1. Urethane Prepolymer [Component A]

The hydroxyl terminal urethane prepolymer used in the present invention is reacted by mixing an aromatic or aliphatic isocyanate with a polyol, a chain extender, etc. in an appropriate ratio, and includes at least two or more hydroxyl groups at both ends, preferably two or four or less. It is a high molecular compound, and is a semisolid or solid state at room temperature. In the urethane prepolymer, less than two terminal hydroxyl groups harden well, and if more than four, crosslinking degree is too high, flexibility is poor, curing reaction is too fast, and work efficiency is lowered due to viscosity increase.

The hydroxyl end prepolymers have a melt viscosity at 60 ° C. of 1,000 to 20,000, preferably 2,000 to 12,000 more preferably 3,000 to 8,000 cps. If the melt viscosity is less than 1,000 cps at 60 ° C., it is not preferable because uniform thickness adjustment is difficult, shape stability is poor, and crosslinking-curing reaction is too slow, resulting in poor physical properties. On the other hand, if it exceeds 20,000cps, there is a limit to mixing uniformly in a high-speed reactive type machine and it is difficult to secure production stability because it is difficult to control uniform gelation time due to difficulty in uniform discharge. In addition, the urethane prepolymer may be efficiently melted at 60 ° C. or less in consideration of molding processability, production efficiency, gelation time, and reactivity.

Polyols used to synthesize the urethane prepolymer may be used alone or a mixture of two or more selected from polyester-based polyols, polyether-based polyols, lactone-based polyols, polycarbonate polyols. This urethane prepolymer has a long gelling time, so it has excellent work stability, and when it is heated above a certain temperature, crosslinking and curing reactions occur easily. A solvent-free urethane type binder having excellent heat resistance, hydrolysis resistance, peel strength, and the like can be provided.

For this purpose, the preferred component mixing ratio of the polyol is 10 to 35 parts by mass of the crystalline polyether polyol having a molecular weight of 800 to 5,000 or more bifunctional groups, 20 to 55 parts by mass of the crystalline polyester polyol, and 10 to 30 parts by mass of the amorphous polyester polyol. , 0.3 to 5 parts by mass of a flame retardant polyol, and 1 to 8 parts by mass of a chain extender.

The crystalline polyether polyol is a polytetramethylene ether polyol, a caprolactone ether polyol or a polycarbonate polyol, and the like, and the crystalline polyester polyol is an ethylene glycol (EG), butanediol (BD), having an even number of repeating units, Synthetic polyols with diols such as hexanediol (HD), adipic acid (AA), sebaic acid (SA), and terephthalic acid.

Amorphous polyester polyols are synthetic polyols of methylpentanediol (MPD) and adipic acid (AA), synthetic polyols of neopentyl glycol (NPG) and adipic acid (AA), neopentyl glycol (NPG), diethylene glycol (DEG) And a synthetic polyol of adipic acid (AA).

As the chain extender, low molecular weight diols having an even number of repeating units, which are advantageous for increasing the degree of crystallinity, are used. For example, ethylene glycol, propylene glycol, 1.4-butane diol, 1.6-hexanediol and the like can be used alone or in combination. As another chain extender, a polyfunctional low molecular weight polyol having a number average molecular weight of 650 or less and a functional group of 3 or more can be used in combination to increase the degree of crosslinking and curing.

The hydroxyl terminal prepolymer as described above has a characteristic of expressing rigidity and strong cohesive force while having an appropriate melting temperature and viscosity, and is relatively less stored than conventional isocyanate terminal end prepolymers because it is less likely to be deformed by moisture. And easier handling.

In addition, the flame-retardant polyol does not require any additional process of adding a flame retardant separately by adjusting a stable urethane structure by reacting a reactive phosphate ester-based polyol having no harmful gas and excellent flame retardant effect during urethane prepolymer production. It is designed to have a performance.

As the isocyanate used in the synthesis of the urethane prepolymer, 4.4-diphenylmethane diisocyanate (MDI) is mainly used, but in addition, it is also possible to use isocyanate in combination within the range that does not impair the effect of the present invention. Compounds, such as MDI, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (H ₁₂ MDI), xylene diisocyanate (XDI), can be utilized, but are not limited to this.

It is preferable to make the hydroxyl group terminal prepolymer which is [component A] react with 1.5 to 4.0 equivalent of polyol with respect to 1 equivalent of isocyanate. If the polyol equivalent to less than 1.5 equivalents of the isocyanate, the end of the prepolymer is difficult to terminate the hydroxyl group, the number average molecular weight is greatly increased and the operation is difficult as the melt viscosity is too high, and if the polyol equivalent is 4.0 or more, the number average molecular weight is small The problem that the physical property after reaction molding falls.

Moreover, a filler can also be added to the said hydroxyl terminal prepolymer as needed. As said filler, calcium carbonate (CaCO3) and mica ( ₃ micrometers or less) of 3 micrometers or less. Inorganic fillers such as talc and clay are preferred. The inorganic filler is mixed in the form of powder into the hydroxyl terminal prepolymer, and the powder crystal serves as a nucleating agent to induce rapid nucleation at low temperature. In addition, it promotes nucleation even near the melting point of the polymer to induce rapid crystallization, thereby speeding up the solidification rate, which is advantageous for improving productivity.

The fillers may be used alone or in combination of two or more, and the amount thereof is suitably used in an amount of 0.1 to 10 parts based on 100 parts by mass of the urethane prepolymer. If the amount of the filler used is less than 0.1 part by mass, the effect of promoting crystallization is lowered. On the other hand, when the amount of the filler is used is more than 10 parts by mass, mechanical properties such as peeling strength and tear strength of the urethane binder may be lowered, which is not preferable.

2. Isocyanate functional group-containing compound [component B]

Examples of the isocyanate compound which acts as a crosslinking agent of the hydroxyl group-terminated urethane prepolymer include carbodiimide-modified MDI, biuret-type HDI, isocyanurate-type HDI, modified IPDI, or isocyanate-group terminal having an isocyanate functional group capable of reacting with a hydroxyl group in the molecular structure. The prepolymer may be used alone or in combination of two or more thereof.

The isocyanate compound uses 1.05 to 2.8 equivalents based on 1 equivalent of the hydroxyl group terminated urethane prepolymer [component A]. Less than 1.05 equivalent to 1 equivalent of the urethane prepolymer, the degree of crosslinking and curing is insufficient, resulting in a decrease in physical properties and heat resistance of the binder. If the amount is more than 2.8 equivalent, the degree of crosslinking is too high, the flexibility is reduced, and a large amount of residual isocyanate is present. Deterioration of chemical properties may cause a problem of inferior product uniformity.

A general aromatic isocyanate-based crosslinking agent has a problem in that the yellowing resistance is bad and the color turns yellow over time. Therefore, in order to improve this problem, biuret type HDI, isocyanurate type HDI or aliphatic isocyanate terminated prepolymer can be used as a crosslinking agent.

3. Urethane Crosslinking Curing Catalyst [Component C]

As the urethane cross-linking curing catalyst, conventionally known amine catalysts such as triethylenediamine and dimethyl cyclohexylamine can be used. Also, active catalysts and blowing catalysts by temperature effective for heating and curing systems and It can also be used together. Examples of the amine catalyst include triethyl amine (trade name: Dabco 33LV), Bis (dimethyl amino ether) (brand name: Dabco BL-11), N, N-dimethyl cyclohexyl amine (Polycat-8), Tris (dimethyl amino propyl amine (Polycat) -9) and the like.

The amount of the urethane gelling catalyst used is 0.01 to 5 parts by mass based on 100 parts by mass of the hydroxyl group urethane prepolymer, and when the amount is less than 0.01 parts by mass, the crosslinking curing reaction is too slow to form a film. This too quickly gels instantaneously, resulting in poor work productivity.

4. Surfactant (Surfactant) [Component C]

Non-silicone-based surfactants are suitable as surfactants that lower the surface tension of the urethane binder sheet, minimize the occurrence of pinholes, and uniformly distribute the pore size. Generally, silicone surfactants are used as surfactants, but since they have a limited compatibility with the catalyst, non-silicone surfactants without polyalkylsiloxane (Si-O) bonds in the molecular structure are used in the present invention. Specifically, Dabco-LK 221, Dabco-LK 443, etc. of Air Products, Inc. are mentioned.

The amount of the foam stabilizer is 0.1 to 10 parts by mass, preferably 0.5 to 6 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the urethane prepolymer. This is because if the content of the foam stabilizer (Surfactant) is less than 0.1 parts by mass, pores are difficult to form, and if more than 10 parts by mass, the pores are formed too much, which results in deterioration of mechanical properties due to excessive pores.

Hereinafter, the flocking artificial leather of the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples. In addition, the part of the following Example and a comparative example shows a mass part unless there is particular notice.

Synthesis of hydroxyl terminal urethane prepolymer

≪ Synthesis Example 1 &

350 parts of polytetramethylene glycol (PTMG, manufactured by BASF) having a number average molecular weight in the reactor, 1,4 butanediol (BG) and the reaction of adipic acid (AA) Synthetic polyol (number average molecular weight 2,000, trade name: K-320 , 450 parts of reaction chemicals, 170 parts of reaction synthetic polyols (number average molecular weight 2,000, trade name: K-400, homochemical products) of neopentyl glycol (NPG) and adipic acid (AA), polypropylene glycol functional group trivalent (PPG, number average molecular weight 400, product name: GP-400, KPX Chemical Co., Ltd.), 20 parts were added and mixed uniformly at 70-80 ° C. for 20 minutes, and then cooled to about 60 ° C. in consideration of exothermic reaction, and then the mixed solution To 70 parts of 4,4-diphenylmethane diisocyanate (MDI, trade name: Cosmonate, Kumho Mitsui) was added, followed by reacting for about 3 hours. Subsequently, 10 parts of flame-retardant polyols (trade name: PO500, manufactured by Hyundai Hi-Chem) were added and reacted to obtain hydroxyl terminal prepolymer-1.

≪ Synthesis Example 2 &

Put 300 parts PTMG, 450 parts K-320, 170 parts K-400, and 20 parts GP-400 having a number average molecular weight of 2,000 in the reactor, and uniformly mix them at 70 to 80 ° C. for 20 minutes, and then consider the exothermic reaction. After cooling to the temperature of C, 70 parts of MDI was added to the mixed solution and reacted for about 3 hours. Subsequently, 13 parts of PO500 were added and reacted to obtain hydroxyl terminal prepolymer-2.

≪ Synthesis Example 3 &

350 parts of PTMG having a number average molecular weight of 2,000, 450 parts of a reaction synthetic polyol (number average molecular weight of 2,000, trade name: K-640, a chemical chemical product) of 1,6 hexanediol (HG) and adipic acid (AA), 170 parts of K-400 and 8 parts of DEG were added and mixed uniformly at 70 to 80 ° C. for 20 minutes, and then cooled to a temperature of about 60 ° C. in consideration of an exothermic reaction, and then 70 parts of MDI were added to the mixture to react for about 3 hours. I was. Subsequently, 13 parts of PO500 were added and reacted to obtain hydroxyl terminal prepolymer-3.

≪ Synthesis Example 4 &

250 parts of PTMG with a number average molecular weight of 2,000, K-320 350, 150 parts of polycarbonate diol (number average molecular weight 2,000, trade name T-6002, manufactured by Asahi Kasahi), 230 parts of K-400, and 20 parts of GP-400 After the mixture was uniformly mixed at 70-80 ° C. for 20 minutes, and cooled to a temperature of about 60 ° C. in consideration of an exothermic reaction, 70 parts of MDI was added to the mixed solution, followed by reaction for about 3 hours, followed by addition of 13 parts of flame-retardant polyol. The hydroxyl terminal terminal prepolymer-4 was obtained.

≪ Synthesis Example 5 &

Reactive synthetic polyol of PTMG with number average molecular weight 2,000 in the reactor, ethylene glycol (EG), 1,4 butanediol (BG) and adipic acid (AA) (number average molecular weight 2,000, K-340, from KK Chemicals) 480 parts, K-400 170 parts, 1,4 BG 6 parts were added and mixed uniformly at 70-80 ° C. for 20 minutes, cooled to about 60 ° C. in consideration of exothermic reaction, and then 70 parts of MDI were added to the mixed solution. After reacting for about 3 hours. Subsequently, 13 parts of flame-retardant polyols were added and reacted to obtain hydroxyl terminal prepolymer-5.

Production of Solvent-Free Urethane Type Binder Sheet

≪ Example 1 >

100 parts of the hydroxyl terminal urethane prepolymer-1 are heated and melted at 60 ° C., and then maintained at 60 ° C. in a thermal container. Then, 13 parts of isocyanate compound (trade name: Cosmonate LL, Kumho Mitsui Chemicals, Modified MDI, NCO Content 28.5%) and 0.8 part of trade name Polycat-8 (manufactured by Air products) as a curing catalyst, and a foam stabilizer (trade name Dabco LK-443). ) 2.0 parts of the mixed liquid was transferred to a high speed stirring molding machine by a separate line, followed by high speed stirring at 5,000 rpm for 3 seconds to obtain a mechanical reaction mixture. The reaction mixture was coated on a release paper with a thickness of 350 μm, crosslinked and cured by heating at a temperature of 100 to 140 ° C. for 3 minutes, and then left at about 50 ° C. for 24 hours to form a solvent-free urethane binder sheet. Got.

<Example 2>

A binder sheet was prepared under the same conditions as in Example 1 utilizing the hydroxyl terminal prepolymer-2 of Synthesis Example 2.

<Example 3>

A binder sheet was prepared under the same conditions as in Example 1, utilizing the hydroxyl terminal prepolymer-3 of Synthesis Example 3.

<Example 4>

A binder sheet was prepared under the same conditions as in Example 1, using the hydroxyl terminal prepolymer-4 of Synthesis Example 4.

<Example 5>

A binder sheet was prepared under the same conditions as in Example 1, utilizing the hydroxyl terminal prepolymer-5 of Synthesis Example 5.

<Example 6>

Under the same conditions as in Example 1, a binder sheet having micropores was prepared while injecting nitrogen gas, which is a non-reactive gas, into a high-speed reaction molding machine in an amount of 0.1 l / min.

&Lt; Comparative Example 1 &

It carried out under the same conditions as in Example 1 described in WO 2005/083173 and the like. 100 parts of isocyanate group terminated urethane prepolymer (PTMG-2000, HG / AA-2000, XDI type prepolymer, NCO content 2.1%) were heated and melted at 120 ° C. to maintain 120 ° C. in an insulated tank, and 12 parts of PPG-5,000 and colorant 8 The parts were mixed uniformly and then stirred at 5,000 rpm for 3 seconds in a high speed stirring molder to obtain a mechanical reaction mixture. The mechanical reaction mixture was discharged onto a release paper and coated to a thickness of 350 μm, and left for 72 hours at a relative humidity of 65% and room temperature to obtain a binder sheet.

Comparative Example 2

It was carried out under the same conditions as in Example 1 described in WO 2001/96435 and Korean Patent Registration 10-0573044. 100 parts of isocyanate group terminal urethane prepolymer (NCO Prepolymer / PTMG-2000, PPG-6000 (trifunctional group), NCO content 12.5%) and a crosslinking curing agent (PPG-2000 / PPG-6000 (trifunctional group) / 1, BG / 70.46 parts of catalyst, 70/15/15 / 0.06 mass ratio) was stirred at 5,000 rpm for 3 seconds in a high speed stirring molding machine by a separate line to obtain a mechanical reaction mixture. The mechanical reaction mixture was discharged onto a release paper and coated to a thickness of 350 μm, and left for 72 hours at a relative humidity of 65% and room temperature to obtain a binder sheet.

<Experimental Example 1>

Example 1 to Example 6 and the binder sheet produced by the manufacturing method of Comparative Example 1 and Comparative Example 2 after the physical property test as follows, the results are shown in Table 1 below.

Tensile characteristics

Tensile properties of the binder sheet were measured based on KS M 6782, ASTM D-412, and JIS K7311.

Heat resistance

After the binder sheet was subjected to a heat test for 3 weeks at 120 ° C., tensile properties were measured based on KS M 6782, ASTM D-412, and JIS K7311.

Hydrolysis Resistance

After the binder sheet was subjected to hydrolysis resistance test at 70 ° C. temperature and 95% RH for 3 weeks, tensile properties were measured based on KS M 6782, ASTM D-412, and JIS K7311.

Peel Strength

A 25 mm wide hot melt cloth tape was heat-sealed at 130 ° C. for 5 seconds on both sides of the binder sheet, and the interlaminar peel strength of the sheet was measured based on KS M 0533 and JIS K 6854.

Flame Retardant

The binder sheet was evaluated based on JIS D1201, KS K0583 "Combustion Test Method for Organic Materials for Automobile Interior".

-Delayability: Combustion rate exceeded 100㎜ / min

-Retardance: Combustion rate is 100mm / min or less

-Self-extinguishing: Within 50mm from the standard line and digested within 60 seconds

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Aging period (hours) 72 120 24 24 24 24 24 24 Seal
characteristic Modulus
(Kg _f / cm ² ) 13.2 7.8 10.6 10.4 12.6 11.8 11.2 9.6 The tensile strength
(Kg _f / cm ² ) 30.6 19.8 32.6 31.0 34.2 33.5 32.0 28.0 Elongation (%) 650 850 720 750 710 716 730 680 Heat resistance Modulus
(Kg _f / cm ² ) 12.1 6.8 10.2 10.0 12.4 11.6 11.1 9.4 The tensile strength
(Kg _f / cm ² ) 28.3 17.2 31.5 30.4 33.7 33.0 31.6 27.6 Elongation (%) 602 730 690 728 703 708 720 668 I can
Degradable Modulus
(Kg _f / cm ² ) 12.1 6.6 10.1 10.0 12.5 11.5 11.1 9.3 The tensile strength
(Kg _f / cm ² ) 28.1 17.2 31.5 30.3 33.7 33.0 31.4 27.5 Elongation (%) 598 725 688 726 702 706 721 665 Peel Strength (Kg _f / cm ² ) 2.6 1.7 3.3 3.2 3.6 3.5 3.4 2.9 Burning speed 95 92 32 33 31 32 33 29

Looking at the physical property results of the solvent-free urethane-type binder sheet described in Table 1, in the case of Examples 1 to 6 according to the manufacturing method of the present invention hydrolysis resistance, in addition to physical properties such as tensile strength, elongation and peel strength at break In terms of heat resistance, it can be seen that it has superior characteristics compared to Comparative Examples 1 and 2 corresponding to the prior art.

In addition, the aging time it can be seen that Examples 1 to 6 of the present invention is significantly faster than Comparative Examples 1 and 2, which is excellent in crosslinking and curing properties of the urethane binder according to the present invention and fast solidification rate form stability Since this is excellent may mean that the processing time is shortened. On the other hand, in the case of Comparative Examples 1 and 2, the mechanical properties and peeling strength are also lowered, and the aging time is too long.

In addition, in the results of flame retardancy test, Examples 1 to 6 according to the present invention exhibited much superior flame retardant effect in the combustion rate measurement performed by the method of measuring measurement of Hyundai-Kia Motors MS-300-08 and KSB 9152-1978, which is a law of the Ministry of Construction and Transportation. Can be confirmed.

Manufacturing of Floating Artificial Leather Products

&Lt; Example 7 >

100 parts of the urethane prepolymer-1 of Synthesis Example 1 was heated and melted at 60 ° C., and maintained at 60 ° C. in an insulated container, followed by an isocyanate compound (Cosmonate LL: Kumho Mitsui Chemicals, Modified MDI, NCO Content 28.5%). 13 parts and 0.8 parts of curing catalyst (Polycat-8) and 2.0 parts of foam stabilizer (Dabco LK-443) were added and transferred to a high speed stirring molding machine by a separate line, followed by high speed mixing for 3 seconds at a stirring speed of 5,000 rpm. To obtain a mechanical reaction mixture.

The mechanical reaction mixture was formed into a binder layer by discharging the urethane dispersed in a 150 μm thickness on the impregnated fiber substrate (nonwoven fabric), and then laminating a fiber pile on the binder layer upper surface and having a temperature gradient of 100 to 140 ° C. The mixture was heated to dry for 3 minutes to cross-cure the binder layer, and then brushed, and left at 50 ° C. for 24 hours to obtain a flocking product.

&Lt; Example 8 >

Using the hydroxyl terminal terminal prepolymer-2 of Synthesis Example 2 was prepared in the same manner as in Example 7.

&Lt; Example 9 >

Using the hydroxyl group terminal prepolymer-3 of Synthesis Example 3 was prepared in the same manner as in Example 7.

&Lt; Example 10 >

The floating product was prepared in the same manner as in Example 7, using the hydroxyl terminal prepolymer-4 of Synthesis Example 4.

<Example 11>

Using the hydroxyl terminal terminal prepolymer-5 of Synthesis Example 5 was prepared in the same manner as in Example 7.

&Lt; Example 12 >

Under the same conditions as in Example 7, a floating product having micropores was prepared while injecting nitrogen gas, which is a non-reactive gas, into a high-speed reaction molding machine in an amount of 0.1 l / min.

<Comparative Example 3>

It carried out under the same conditions as in Example 1 described in WO 2005/083173 and the like. 100 parts of isocyanate group terminated urethane prepolymer (PTMG-2000, HG / AA-2000, XDI type prepolymer, NCO content 2.1%) were heated and melted at 120 ° C. to maintain 120 ° C. in an insulated tank, and 12 parts of PPG-5,000 and colorant 8 The parts were mixed uniformly and then stirred at 5,000 rpm for 3 seconds in a high speed stirring molding machine by a separate line to obtain a mechanical reaction mixture. The mechanical reaction mixture was discharged on a fibrous substrate (nonwoven fabric) to a thickness of 150 μm to form a binder layer, and then a fiber pile was laminated on the binder layer, and left for 72 hours at room temperature and 65% relative humidity for flocking product. Got.

&Lt; Comparative Example 4 &

It was carried out under the same conditions as in Example 1 described in WO 2001/96435 and Korean Patent Registration 10-0573044. 100 parts of isocyanate group-terminated urethane prepolymer (NCO Prepolymer / PTMG-2000, PPG-6000 (trifunctional group) type prepolymer, NCO content 12.5%) and a crosslinking curing agent (PPG-2000 / PPG-6000 (trifunctional group) / 1, BG / Catalyst, 70/15/15 / 0.06 mass ratio) 70.46 parts by high speed stirring in a high speed stirring molding machine at 5,000 rpm for 3 seconds by a separate line to obtain a mechanical reaction mixture. The mechanical reaction mixture was discharged on a fibrous substrate (nonwoven fabric) with a thickness of 150 μm to form a binder layer, and then a fiber pile was laminated on the binder layer, and left for 120 hours at room temperature and 65% relative humidity for a flocking product. Got.

<Experimental Example 2>

After the physical property test as follows for the flocking product prepared by Examples 7 to 12, and Comparative Example 3 and Comparative Example 4, the results are shown in Table 2 below.

Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 3 Comparative Example 4 Friction fastness ○ ◎ ○ ◎ ◎ ◎ △ ○ Wear resistance ○ ○ ◎ ◎ ◎ ◎ △ ○ Shape stability ○ ○ ○ ○ ○ ◎ ○ △ touch ○ ◎ ◎ ◎ ◎ ◎ △ ○

◎ Very good, ○ Good, △ Bad

As can be seen from the results of Table 2, in the case of Examples 7 to 12 manufactured by the manufacturing method of the present invention in terms of friction fastness and wear resistance, form stability, tactile feeling compared to Comparative Examples 3 and 4 corresponding to the prior art It is excellent and efficient in terms of productivity.

Reference Signs List 1 fiber base layer 2 binder layer 3 pile fiber layer

Claims (19)

(a) a urethane prepolymer having a hydroxyl group having a melt viscosity of 1,000 to 20,000 cps at both ends at 60 ° C. by reacting isocyanate with a polyol mixture composed of crystalline polyol, amorphous polyol, flame retardant polyol, and chain extender [component A] Synthesizing;
(b) melting the urethane prepolymer component at 60 ° C. or below:
(c) A fixed amount of molten urethane prepolymer [component A], an isocyanate compound [component B], and an additive [component C] containing a crosslinking curing catalyst and a foaming agent in a fixed amount in a high-speed reaction molding machine through separate lines. And then stirring and mixing at high speed;
(d) discharging the reaction mixture onto the upper surface of the fiber substrate finely dispersed with water-dispersed urethane, and then performing a knife or comb coating to form a binder layer:
(e) Flocking the fiber pile on the binder layer, crosslinking, curing and brushing under a temperature condition of 80 ℃ to 150 ℃, then lowering to a temperature of 30 to 80 ℃ and post-curing using a solvent-free urethane binder Artificial leather manufacturing method. The polyol component of the urethane prepolymer [component A] is 10 to 35 parts by mass of crystalline polyether polyol having a number average molecular weight of 800 to 5,000 or more, and 20 to 55 parts by mass of crystalline polyester polyol. , 10 to 30 parts by mass of an amorphous polyester polyol, 0.3 to 5 parts by mass of a flame retardant polyol, and 1 to 8 parts by mass of a chain extender. The polycrystalline polyether polyol of claim 1 or 2, wherein the crystalline polyether polyol of the urethane prepolymer [component A] is at least one of polyols present in a solid phase at room temperature, such as polytetramethylene meta polyol, capro ether polyol or polycarbonate polyol Flocking artificial leather manufacturing method using a solvent-free urethane-type binder, characterized in that made. The crystalline polyester polyol of the urethane prepolymer [component A] is a diol such as ethylene glycol (EG), butanediol (BD), hexanediol (HD) having an even number of repeat units, A method for producing flocked artificial leather using a solvent-free urethane-based binder, characterized in that it comprises at least one of polyols present in a solid state at room temperature, such as synthetic polyols such as adipic acid (AA), sebacic acid, terephthalic acid or isophthalic acid. The amorphous polyester polyol of the urethane prepolymer [component A] is a synthetic polyol of neopentyl glycol (NPG) and adipic acid (AA), neopentyl glycol (NPG), diethylene glycol (DEG). Flocking using a solvent-free urethane-based binder, characterized in that at least one of a polyol present in the liquid phase at room temperature, such as a synthetic polyol of a) and adipic acid (AA), a synthetic polyol of methyl pentanediol (MPD) and adipic acid (AA) Artificial leather manufacturing method. The method for producing flocked artificial leather according to claim 1 or 2, wherein the flame retardant polyol of the urethane prepolymer [component A] is a phosphate ester-based polyol. The chain extender of the urethane prepolymer [component A] is a low molecular weight diol or number average molecular weight such as ethylene glycol, 1.2-propylene glycol, 1.4-butane diol, 1.6-nucleic acid diol, or neopentylglycol. The method for producing flocked artificial leather using a solvent-free urethane-type binder, characterized in that the 650 or less and made of at least one of a multifunctional low molecular weight polyol having a functional group of 3 or more. The isocyanate of the urethane prepolymer [component A] according to claim 1 or 2, wherein 4.4-diphenylmethane isocyanate (MDI), modified MDI, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicylo Hexyl methane diisocyanate (H ₁₂ MDI), xylene diisocyanate (XDI) at least one of a synthetic artificial leather manufacturing method using a solvent-free urethane type binder, characterized in that made. The method of claim 1 or 2, wherein the urethane prepolymer [component A] has a melt viscosity in the range of 1,000 to 20,000 melt viscosity at 60 ° C. The method of claim 1 or 2, wherein the urethane prepolymer [component A] is reacted with 1 equivalent of isocyanate at a ratio of 1.5 to 4.0 equivalents of polyol. The method of claim 1, wherein the isocyanate compound [component B] is carbodiimide modified diphenylmethane diisocyanate, biuret type hexamethylene diisocyanate, isocyanurate type hexamethylene diisocyanate, modified isophorone diisocyanate or isocyanate Flocking artificial leather manufacturing method using a solvent-free urethane-type binder, characterized in that consisting of at least one of the terminal end prepolymer. The residual isocyanate group content of the said isocyanate type compound [component B] is 10-35 mass%, The manufacturing method of the artificial artificial leather of Claim 1 or 11 using the solvent-free urethane type binder. The method of claim 1 or 11, wherein the isocyanate compound [component B] is 1.05 to 2.8 equivalents based on 1 equivalent of the urethane prepolymer [component A]. The calcium carbonate (CaCO ₃ ) and mica according to claim 1 or 2 with respect to 100 parts by mass of the urethane prepolymer [component A]. A method for producing flocked artificial leather using a solvent-free urethane-type binder, wherein 0.1 to 10 parts by mass of an inorganic filler selected from talc and clay is further added. The crosslinking curing catalyst [component C] is an amine catalyst such as triethylenediamine and dimethyl cyclohexylamine, and 0.01 to 5 parts by mass is added to 100 parts by mass of the urethane prepolymer [component A]. Flocking artificial leather manufacturing method using a solvent-free urethane type binder. The method according to claim 1, wherein the foam stabilizer [component C] is a non-silicone surfactant having no polyalkylsiloxane (Si-O) bond, 0.1 to 10 parts by mass added to 100 parts by mass of the urethane prepolymer [component A] Flocking artificial leather manufacturing method using a solvent-free urethane type binder characterized in. The non-solvent according to claim 1, wherein the fiber base is a fiber base having micropores formed therein after squeezing a nonwoven fabric impregnated with a non-woven urethane and then thermally and solidified on saturated water vapor. Flocking artificial leather manufacturing method using a urethane-type binder. delete A flocked artificial leather processed product, characterized in that the flocking artificial leather manufactured by the manufacturing method of claim 1 processed to be used as a skin material of shoes, clothing, furniture, interior materials of automobiles.

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