KR20120109062A - Excellent elastic and stretchable hotmelt thermoplastic polyurethane resin as adhesive and superiority flexibility and strong heat resistance protect layer which is thermoplastic polyurethane resin. it is a manufactured using film and manufacturing method - Google Patents

Abstract

PURPOSE: A hot-melt thermoplastic polyurethane resin for adhesion is provided to prevent damage, contraction and deformation of fabric due to heat; to improve elongation; and to have excellent heat resistance. CONSTITUTION: A hot-melt thermoplastic polyurethane resin for adhesion can be obtained by injecting 60-85 weight% of polyol with a molecular weight of 1500-2500, 5-10 weight% of a bifunctional chain extender to the polyol, 35-5 weight% of organic diisocyanate into a mixture; and mix-reacting the mixture. A melting point of the hot-melt thermoplastic polyurethane resin is 80-140°C and elongation is 650-1,200%.

Description

Thermoplastic polyurethane resin for adhesive and adhesive layers with excellent elasticity, thermoplastic polyurethane resin for protective layers with excellent elasticity and heat resistance, and films prepared using the same and methods for producing the same {Excellent elastic and stretchable hotmelt thermoplastic polyurethane resin as adhesive and superiority flexibility and strong heat resistance protect layer which is thermoplastic polyurethane resin. it is a manufactured using film and manufacturing method}

The present invention is polyol, bifunctional in order to block the damage, shrinkage, deformation, etc. of the fabric caused by the heat generated during adhesion in order to be able to select and use the laminated film having the adhesive and the adhesive layer according to the characteristics of the fabric and to improve the elasticity Injected and prepared by chain extension and organic diisocyanate injection-molded flexible hot melt thermoplastic polyurethane resin and film having various melting points between 80 ° C and 140 ° C, polyols, difunctional chain extenders and organic diisocyanates The present invention relates to a thermoplastic polyurethane resin having elasticity and heat resistance having a melting point of 160 ° C. to 230 ° C. and a thermoplastic polyurethane laminated film having excellent heat resistance and elasticity in which a film made of the resin is laminated.

The production of conventional thermoplastic polyurethane resins for hot melts and thermoplastic polyurethane resins is well known in the art. These materials have been found to be useful for numerous applications by spray coating, roll coating, extrusion and injection molding using other known methods, but form different properties, shapes and shapes depending on the mixing ratio and preparation method of the composition. can do.

       Specific prior arts of thermoplastic polyurethane resins for hot melts are disclosed in Korean Patent Application Laid-Open No. 1995-11580 for hot melt adhesives prepared from mixtures of polyester diols, polyoxyalkylene glycols and glycol extenders. Polyurethane resins are disclosed in Korean Patent Publication No. 10-2007-062058, and the melting point disclosed in Korean Patent Publication No. 10-0842218 is adjusted differently and is recycled after use. Although the technical content regarding the manufacturing method is disclosed, the hot-melt polyurethane resin and the film technology which are excellent in elasticity are not disclosed.

Specific prior arts of thermoplastic polyurethane resins having excellent heat resistance include an environmentally friendly and recyclable thermoplastic polyurethane elastomer having a high melting point and a softening point made from a mixture of polyester diols, polyoxyalkylene glycols and glycol extenders. Although specifically disclosed in Korean Patent Publication No. 10-0842218, a description of a thermoplastic polyurethane resin and a film excellent in elasticity and heat resistance is not disclosed.

       As a specific conventional technology for a laminated film, a thermoplastic polyurethane resin for an adhesive and a protective layer, a laminated film manufactured using the same, and a manufacturing method thereof are disclosed in Korean Patent Publication No. 10-0842218, but the present invention Hot melt adhesive polyurethane resin, which can be manufactured by adjusting to various melting points, and heat-resistant thermoplastic polyurethane resin film having excellent elasticity, high melting point and softening point, and being recycled There is a remarkable difference from the problem to provide a laminated film produced by the manufacturing method.

       In recent years, the convergence of high technology such as IT, NT, BT, ET has also been actively made in footwear and clothing parts and materials. The convergence of these technologies has been recognized as a way to check Chinese companies that are eroding the market with low-priced strategies by imitating advanced countries' technology by taking the technology level of the existing shoe parts to the next level.

Recently, the interest in the environment is gradually increasing in the footwear industry. In particular, the big brand in the shoe industry is attempting to switch to the eco-friendly construction process from the manufacturing of shoe parts to the finishing process. In particular, in the adhesion process that is essential for the manufacture of shoes, the conventional oil-based adhesive process has been converted to an aqueous adhesive process that minimizes the use of organic solvents, and the upper part of the shoe has been converted to an eco-friendly hot melt adhesive without sewing. They prefer uppers with excellent comfort and require development of elastic hot melt adhesives.

In addition, hiking boots, golf shoes, snowboard shoes, and related clothing apply high-tech materials such as Gore-Tex. However, if there is a seam in the fabric processing, water leakage may occur along the seam, and thus there is an increasing need and demand for a lamination film that prevents leakage and beautifully covers the appearance. Increasingly, there is a continuing need to improve the requirements for resistance to physical properties such as durability, flexibility, elasticity, antifouling, waterproofing, recycling rate, high abrasion and high burst resistance, and the prior art can be used for these applications. Even if the material can be produced, the demand and research and development for a material having superior elasticity than the material in the prior art still exist as a technical problem to be solved, and it is an object of the present invention to solve such a technical problem.

The problem to be solved by the present invention is a polyol, a bifunctional chain extender and an organic diisocyanate mixed reaction at a predetermined weight percent ratio in order to prevent damage, shrinkage and deformation of the fabric due to heat during adhesion and to improve the elasticity to improve the melting point The present invention provides an adhesive hot melt thermoplastic polyurethane resin prepared by adjusting differently.

Another problem to be solved by the present invention is to protect the adhesive layer and prevent stickiness (Tacky) while preventing the damage, shrinkage and deformation of the fabric by heat during adhesion, high elasticity and high melting point resistant to heat generated during thermal bonding It is to provide a thermoplastic polyurethane resin for a protective layer having excellent heat resistance.

Another problem to be solved by the present invention is to prepare a hot-melt thermoplastic polyurethane resin having excellent melting point prepared by different melting point by adjusting the melting point to produce a film having an adhesive layer suitable for the fabric, stretch and heat resistance as a protective layer By manufacturing excellent thermoplastic polyurethane resin, it prevents damage, shrinkage and deformation of fabric due to heat during adhesion, and prevents environmental pollution caused by solvent generated in manufacturing organic solvent type polyurethane, and causes the generation of substances harmful to human body. The present invention provides an environment-friendly adhesive film, a laminated film, and a method of manufacturing the same, which are blocked and recycled.

In order to solve the problem of the present invention to prevent the damage, shrinkage, deformation, etc. of the fabric due to heat generated during the adhesion in order to be able to select and use the laminated film having the adhesive and the adhesive layer suitable for the fabric, the molecular weight in order to improve the elasticity Inject 60 to 85 wt% of the polyol of 1500 to 2500, mix 5 wt% to 10 wt% of the bifunctional chain extender, and inject 35 wt% to 5 wt% of the organic diisocyanate. The polyol, the bifunctional chain extender, and the organic diisocyanate react with each other to produce a mixture, and then the melting point is 80 ° C to 140 ° C (80 ° C, 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C). It is to provide a hot-melt thermoplastic polyurethane resin for adhesion with various melting points and excellent elasticity.

Another solution of the present invention is to prepare a butanediol adipate-based polyesterdiol (butanediol), butanediol (1, in order to protect the adhesive layer, to prevent sticky (tacky) and to be resistant to heat generated during thermal bonding 4BG), hydroquinone ethynol ether (HQEE) is mixed at a predetermined ratio and stirred at a predetermined temperature or more, and mixed and prepared by injecting diphenylmethane diisocyanate (MDI) while the mixed composition is maintained in a liquid phase. To provide a thermoplastic polyurethane resin excellent in stretch and heat resistance of 160 ℃ to 230 ℃.

      Another solution of the present invention is an adhesive and adhesive film, the polyol having a molecular weight of 1500 to 2500, difunctional chain extender, organic diisocyanate and isocyanate are mixed and reacted at a constant weight percent ratio to adjust the melting point Differently manufactured hot melt thermoplastic polyurethane film for elastic bonding, and can be stretched in the same way as the stretching of the fabric, and to prevent the damage, shrinkage, deformation, etc. of the fabric due to heat during adhesion using an adhesive suitable for the type of fabric, organic solvent The present invention provides an environmentally friendly adhesive film and a method for manufacturing the same, which can prevent environmental pollution by a solvent generated during the production of a type polyurethane, fundamentally block generation of a substance harmful to a human body, and be recycled.

Another solution of the present invention is an adhesive layer, a polyol having a molecular weight of 1500 to 2500, a bifunctional chain extender, an organic diisocyanate and an isocyanate are mixed and reacted at a predetermined weight% ratio to adjust the melting point to differently stretch the adhesive. Thermomelt thermoplastic polyurethane film for the production, and as a protective layer, a thermoplastic polyurethane having excellent elasticity and heat resistance by mixing and reacting a polyol having a molecular weight of 1500 to 2500, a bifunctional chain extender, an organic diisocyanate and an isocyanate at a constant weight% ratio After the film is manufactured, the laminated film is manufactured by laminating a hot melt thermoplastic polyurethane film and a thermoplastic polyurethane film, and using the hot melt thermoplastic polyurethane resin having different melting points, the same elasticity as that of the fabric, and an adhesive suitable for the fabric type. Laminated film with layers It prevents damage, shrinkage and deformation of fabric by heat during adhesion, and prevents environmental pollution caused by solvent generated when manufacturing organic solvent type polyurethane, and fundamentally blocks the generation of harmful substances to human body, and recycles This is to provide an environmentally friendly laminated film and a method of manufacturing the same.

The present invention has an advantageous effect of obtaining excellent elasticity by mixing the polyol, the bifunctional chain extender, and the organic diisocyanate at a predetermined weight% ratio to adjust the melting point to prepare hot-melt thermoplastic polyurethane resin for adhesion differently.

Another effect of the present invention is to provide a thermoplastic polyurethane resin having a high melting point and elasticity to be used as a protective layer for protecting against heat generated during thermal bonding to protect the adhesive layer and to prevent stickiness. .

      Another effect of the present invention is to mix the polyol, difunctional chain extender, organic diisocyanate and isocyanate in a constant weight percent ratio to adjust the melting point to produce different stretch hot melt thermoplastic polyurethane film, the same as the stretching of the fabric It can be stretched and stretched to prevent the damage, shrinkage and deformation of the fabric caused by heat during adhesion, and to prevent the environmental pollution caused by solvent generated during the production of organic solvent type polyurethane, It is to block the generation of harmful substances.

Another effect of the present invention is to adjust the melting point to produce a flexible hot melt thermoplastic polyurethane film having a different melting point, and laminated with a thermoplastic polyurethane film having elasticity and heat resistance to produce a laminated film, the same elasticity as the fabric It prevents damage, shrinkage and deformation of fabric by heat during adhesion by manufacturing laminated film with adhesive layer suitable for the characteristics of fabric, and environmental pollution caused by organic solvent generated in manufacturing organic solvent type polyurethane It is to prevent the generation of substances harmful to the human body, and to enable recycling.

1 is a stretchable hot melt thermoplastic polyurethane resin prepared according to Examples 1 to 6 of the present invention, the artificial leather and the mesh fabric of the film prepared according to Examples 10 to 15 at a predetermined temperature, pressure and time. It is a photograph that measures the adhesive strength by giving a bond.
FIG. 2 is a photograph taken with an electron microscope at 300 times magnification of a laminated film having elasticity and heat resistance prepared according to Example 19 according to the present invention.
3 is a photograph taken with an electron microscope (Micro Scope) to enlarge the thickness of the protective layer of the laminated film with elasticity and heat resistance prepared according to Examples 19 to 24 of the present invention 300 times.

Hereinafter, the present invention will be described in detail. The present invention is to extend the polyol, bifunctional chain to block the damage, shrinkage, deformation, etc. of the fabric caused by the heat generated during the adhesion to improve the elasticity in order to be able to select the laminated film having a suitable adhesive and adhesive layer for the fabric Hot melt thermoplastic polyurethane resin for adhesiveness having various melting points by mixing and reacting the agent and the organic diisocyanate at a predetermined weight% ratio, a film manufactured using the same, a method for manufacturing the same, waterproofing and decorating sports shoes, and clothing It is proposed to prevent leakage along the seam of and to coat the appearance beautifully.

The category of the present invention relates to a thermoplastic polyurethane resin having heat resistance for adhesion, adhesive and protective layer excellent in elasticity, a film and a laminated film produced using the same, and a manufacturing method thereof.

In order to achieve this, the polyol, the bifunctional chain extender, and the organic diisocyanate are mixed and reacted at a predetermined weight% ratio to adjust the melting point to prepare a stretchable hot melt polyurethane resin and a film having different melting points. .

In addition, a thermoplastic polyurethane resin having elasticity and heat resistance for protecting the adhesive layer made of the adhesive hot melt polyurethane resin, preventing stickiness, and protecting against heat generated during thermal bonding is prepared.

The laminated thermoplastic polyurethane resin and the heat-resistant thermoplastic polyurethane resin prepared above are laminated to each other to provide a laminated film prepared by maintaining a predetermined time by applying a constant pressure at a predetermined temperature and a manufacturing method thereof.

Hereinafter, the configuration, various embodiments, and operations of the present invention will be described, and the configuration and operation of the present invention will be described by at least one or more embodiments, whereby the technical spirit of the present invention and its core configuration and operation will be described. It is not limited.

Prior to the detailed description of the configuration and operation of the present invention, the technical details related to the present invention are described first.

Polyurethane is a kind of polymer which contains a urethane bond in a main chain. Polyurethane is a urethane bond formed by polycondensation of the hydroxyl group (-OH) of the polyol and the isocyanic acid group (-NCO) of the isocyanate, and the properties of the polyurethane obtained vary depending on the properties of the polyol and isocyanate used.

In particular, conventional polyols include polyester polyols and polyether polyols, and polyester polyols include lactone polyester polyols and adipic acid polyester polyols, and adipic acid polyester polyols are multifunctional carboxyl. Obtained by the polymerization of an acid compound and a polyfunctional alcohol compound, adipic acid as a polyfunctional carboxylic acid compound and diol or triol as a polyfunctional alcohol compound are used.

However, polyurethanes using conventional polyester polyols exhibit excellent properties in mechanical strength, processability, heat resistance, abrasion resistance, and economic efficiency, but polyurethanes using polyether polyols in chemical resistance, elasticity, cold resistance, water resistance and specific gravity, etc. There is a disadvantage in that it shows poor characteristics.

Polyether-based polyurethanes, on the other hand, are mixed with ethylene oxide to some extent to form a polyether, and the OH groups at both ends are reacted with toluylene diisocyanic acid to make a high molecular weight polyurethane.

In addition to the mechanical strength, processability, heat resistance, abrasion resistance and economic efficiency expected in polyurethanes using polyester polyols, the physical properties such as chemical resistance, elasticity, cold resistance, water resistance and specific gravity expected in polyurethanes using polyether polyols are improved. To this end, the development of new polyurethanes is required.

The present invention is to solve the problems of the prior art described above.

The present invention is largely divided into three groups of inventions, and the first invention is a stretchable hot melt thermoplastic polyurethane resin and a hot melt thermoplastic adhesive prepared by different melting points by adjusting the melting point for use as an adhesive and an adhesive layer. The present invention relates to a film made of a polyurethane resin, and a second invention relates to a thermoplastic polyurethane resin and a film made of a thermoplastic polyurethane resin manufactured to have excellent stretch and heat resistance for use as a protective layer. A laminated film obtained by manufacturing the stretchable hot melt thermoplastic polyurethane resin as a film having a predetermined thickness and forming an adhesive layer, and manufacturing a thermoplastic polyurethane resin having stretch and heat resistance as a film having a predetermined thickness and laminating it as a protective layer; It is divided into the manufacturing method.

It looks at the specific technical configuration of the present invention.

In a specific technical configuration according to the present invention, the stretchable hot melt thermoplastic polyurethane resin having the first invention is a 60 to 85% by weight of a polyol having a molecular weight of 1500 to 2500, and a bifunctional chain extender 2 5 to 10% by weight of the species are mixed and 35 to 5% by weight of the organic diisocyanate is injected, followed by mixing with a stirrer, a flexible adhesive hot melt having various melting points between 80 ° C and 140 ° C. A thermoplastic polyurethane resin is prepared.

The film made of the stretch adhesive hot melt thermoplastic polyurethane resin is prepared with a thickness of 50 to 2,000 with the prepared stretch adhesive hot melt thermoplastic polyurethane resin.

The thermoplastic polyurethane resin prepared to have excellent elasticity and heat resistance, which is the second invention, is injected with 60 to 85 wt% of a polyol having a molecular weight of 1500 to 2500, and mixed with a bifunctional chain extender to 5 to 10 wt% Injecting, 35% by weight to 5% by weight of the organic diisocyanate, and then mixed with a stirrer to prepare. In this case, when the polyol, the difunctional chain extender, and the organic diisocyanate are reacted with each other by varying the composition ratio, the thermoplastic polyurethane resin having excellent melting point and heat resistance of 160 ° C to 230 ° C can be obtained.

The film made of the thermoplastic polyurethane resin having excellent stretch and heat resistance is made of a thermoplastic polyurethane resin having excellent stretch and heat resistance with a thickness of 50 μm to 2,000 μm.

The third invention is an adhesive layer made of a film having a thickness of 50 to 2,000 between the elastic adhesive hot melt polyurethane resin prepared in the first invention, and a thermoplastic polyurethane resin having excellent elasticity and heat resistance made in the second invention of 30 μm. After laminating a protective layer made of a film having a thickness between 2,000 μm and 2,000 μm, heat and pressure are applied for a predetermined time.

The polyols used as the composition of the stretchable adhesive hot melt thermoplastic polyurethane resins according to the present invention are conventional types of polyester diols, polyether diols and polycarbon diols, and the like, which are known in the art related to the present invention. It is possible to prepare a thermoplastic polyurethane having a variety of properties by using the selected or selected by mixing two or more, the polyester diol includes both lactone-based polyester diols and adipic acid-based polyester diols.

The diisocyanate compound used as the composition of the stretchable adhesive hot melt thermoplastic polyurethane resin according to the present invention is the same or similar to that used for preparing a conventional polyurethane, and the diisocyanate is composed of aromatic isocyanates or aliphatic isocyanates, and diphenyl Select one of methane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or use a mixture of two or more of these selected. The thermoplastic polyurethane resin having a variety of properties can be prepared.

The bifunctional chain extender used in the composition of the stretchable hot melt thermoplastic polyurethane resin according to the invention is the same or similar to that used in the preparation of conventional polyurethanes. The bifunctional chain extender is ethylene glycol (EG), diethylene glycol (DEG), butanediol (1.4BG), hexanediol (1.6HG), neopentylglycol (NPG), dimethylcyclonucleic acid dimethinol (CHDM) , Ditets such as polytetramethylene ether glycol (PTMG, Poly THF), hydroquinone ethynol ether (HQEE), methylene pentane diol (MPD), and two or more organic functional groups (functional groups) capable of reacting with isocyanate compounds. Linear organo-functional Polysiolxane, or any one of the above-mentioned diols and polysiloxanes, or a mixture of two or more of them, and a mixture of two or more of them. Stretch hot melt thermoplastic polyurethane resins having various melting points between 140 ° C can be prepared.

The hot-melt thermoplastic polyurethane resin for elastic bonding according to the present invention is prepared according to a conventional thermoplastic polyurethane manufacturing method, and the conventional manufacturing method is a batch method, a continuous polymerization (reactive extrusion) method, a semi-continuous polymerization It includes the (Belt) method, it can be used selected from these.

The polyol used as the composition of the thermoplastic polyurethane resin having excellent elasticity and heat resistance for use as the protective layer according to the second invention is the same as the polyol used in the composition of the elastic adhesive hot melt thermoplastic polyurethane resin, so as to avoid overlapping substrates. To omit them.

The diisocyanate compound used as the composition of the thermoplastic polyurethane resin having excellent elasticity and heat resistance for use as the protective layer according to the second invention is the same as the diisocyanate compound used in the composition of the hot melt thermoplastic polyurethane resin for elastic bonding. Omitted to avoid duplicate descriptions.

The bifunctional chain extender used as the composition of the thermoplastic polyurethane resin having excellent elasticity and heat resistance for use as the protective layer according to the second invention is a bifunctional chain extension used in the composition of the elastic adhesive hot melt thermoplastic polyurethane resin. Since it is the same as the agent, it is omitted in order to avoid duplicate descriptions.

The thermoplastic polyurethane prepared by mixing the composition of the thermoplastic polyurethane resin excellent in elasticity and heat resistance for use as a protective layer prepared according to the present invention is produced according to a conventional thermoplastic polyurethane manufacturing method, a conventional manufacturing method Silver includes a batch method, a continuous polymerization (reactive extrusion) method and a semi-continuous polymerization (Belt) method, one of these may be selected and used.

Films and laminated films prepared by laminating a stretchable hot melt thermoplastic polyurethane resin prepared according to the present invention and a thermoplastic polyurethane resin excellent in elasticity and heat resistance for use as a protective layer are heat and pressure, which is a conventional method for manufacturing a film. To prepare.

More specifically, the hot melt thermoplastic polyurethane film as the adhesive layer and the adhesive layer and the thermoplastic polyurethane film and the laminated film having excellent elasticity and heat resistance as the protective layer are the single screw extruder whose extrusion molding method is the screw method. ), Twin screw extruder, and multi screw extruder, and select one of the following: Manifold type die, Tee type die, Coat hanger type die It can be produced by a method of selecting any one of the manufacturing method, a method of manufacturing by a non-screw roll (Calender) type extruder or a method of manufacturing by blow molding (Blow Molding) method.

A specific embodiment according to the present invention will be described.

<Examples>

In a specific embodiment according to the present invention maintains the mixing ratio existing within the numerical range of the invention divided into the first invention to the third invention described above with a stretchable thermoplastic polyurethane resin for hot melt adhesive and elasticity The composition of the thermoplastic polyurethane resin for protective layers is prepared.

The specific gravity, hardness, tensile strength, tear strength, heat resistance, and the like of the thermoplastic polyurethane resin for the adhesive and the hot melt for the adhesive layer prepared using the prepared composition, and the thermoplastic polyurethane resin for the protective layer, and the film and the laminated film prepared using the same. Measure properties such as melting point, adhesion, and surface thickness after adhesion.

The following embodiments illustrate one example for illustrating the present invention and should not be understood as limiting the scope of protection of the present invention.

&Lt; Example 1 >

Example 1 is one of the specific examples of the production of the thermoplastic polyurethane resin for the adhesive and the hot melt for the adhesive layer, 78.26% by weight of a butanediol adipate-based polyesterdiol (Poly Butanediol Adipate) having a molecular weight of 2,200 was injected into the stirrer, 2.8% by weight of butanediol (1,4BG) was injected, and 0.81% by weight of pentanediol (NPG) was injected, followed by stirring and mixing with a conventional stirrer at 80 ° C maintaining all three compositions. %, And 18.14% by weight of diphenylmethane diisocyanate (MDI) is injected at 60 ° C. to maintain a liquid phase, followed by mixing to obtain a polymer, or at a mixing ratio of the composition at a temperature at which all four compositions form a liquid phase. At the same time, the mixture was stirred and mixed to obtain a polymer, and then prepared into pellets using a twin screw extruder.

Melting point of the stretch adhesive hot melt thermoplastic polyurethane resin prepared according to Example 1 is relatively low, such as 70 ℃ to 80 ℃.

&Lt; Example 2 >

Example 2 is another one of the specific examples of the thermoplastic polyurethane resin for the adhesive and the hot melt for the adhesive layer, 76.15% by weight of a butanediol adipate-based polyesterdiol (Poly Butanediol Adipate) having a molecular weight of 2,000 Inject 3.3 wt% butanediol (1,4BG), and inject 0.95 wt% of pentanediol (NPG), and then mix all three compositions by stirring with a stirrer at 80 ℃ to maintain a liquid phase, the mixed composition 80.4 wt% 19.6% by weight of diphenylmethane diisocyanate (MDI) was added at about 60 ° C. to maintain a liquid phase, and mixed to obtain a polymer, or the mixing ratio of the above compositions at a temperature where all four compositions form a liquid phase. Simultaneously added and mixed to obtain a polymer, it was prepared as a pellet (Pallet) using a twin screw extruder.

Melting point of the stretch adhesive hot melt thermoplastic polyurethane resin prepared according to Example 2 is a temperature of about 30 ° C. higher than Example 1 to about 100 ° C. to 110 ° C.

Example 3

Example 3 is another one of the specific examples of the thermoplastic polyurethane resin for the adhesive and the hot melt for the adhesive layer, 73.68% by weight of a butanediol adipate-based polyesterdiol (Poly Butanediol Adipate) having a molecular weight of 2,000 Butanediol (1,4BG) is injected 3.88% by weight, and pentanediol (NPG) is injected into 1.12% by weight and then all three compositions are stirred and mixed with a stirrer at 80 ℃ to maintain the liquid phase, the mixed composition 78.69% by weight And diphenylmethane diisocyanate (MDI) 21.31% by weight at about 60 ℃ to maintain a liquid phase to obtain a polymer, or the mixing ratio of the composition at a temperature at which all four compositions form a liquid phase Simultaneously added to the mixture was mixed with a stirrer to obtain a polymer, it was prepared as a pellet (Pallet) using a twin screw extruder.

Melting point of the stretch adhesive hot melt thermoplastic polyurethane resin prepared according to Example 3 is a temperature of about 20 ℃ higher than Example 2 to 120 ℃ to 130 ℃.

Example 4

Example 4 is another one of the specific examples of the thermoplastic polyurethane resin for the adhesive and the hot melt for the adhesive layer, 73.84% by weight of butanediol / hexanediol adipate-based polyesterdiol (Poly Butanediol / Hexandiol Adipate) having a molecular weight of 2,500 Inject to a stirrer, but 3.83% by weight of butanediol (1,4BG), and injected into 3.89% by weight of polysiloxane (Dimethyl Siloxane Hydroxyalkyl Terminated) and then mixed all three compositions by stirring with a stirrer at 80 ℃ to maintain a liquid phase , 81.56% by weight of the mixed composition, and 18.44% by weight of diphenylmethane diisocyanate (MDI) was added at about 60 ° C. to maintain a liquid phase, and mixed to obtain a polymer, or all four compositions form a liquid phase. At the same time at a mixing ratio of the composition at the temperature and mixed with a stirrer to obtain a polymer, using a twin screw extruder Prepared by pellets.

Melting point of the stretch adhesive hot melt thermoplastic polyurethane resin prepared according to Example 4 is the same temperature as in Example 1 to about 70 ℃ to 80 ℃.

Example 5

Example 5 is another one of the specific examples of the thermoplastic polyurethane resin for the adhesive and the hot melt for the adhesive layer, 71.86% by weight of butanediol / hexanediol adipate-based polyesterdiol (Poly Butanediol / Hexandiol Adipate) having a molecular weight of 2,500 Was injected into a stirrer, butanediol (1,4BG) was injected 4.44% by weight, polysiloxane (Dimethyl Siloxane Hydroxyalkyl Terminated) was injected into 3.78% by weight and then all three compositions were stirred and mixed with a stirrer at 80 ℃ to maintain a liquid phase , 80.08% by weight of the mixed composition, and 19.92% by weight of diphenylmethane diisocyanate (MDI) were added at about 60 ° C. to maintain a liquid phase, and mixed to obtain a polymer, or all four compositions form a liquid phase. At the same time at a mixing ratio of the composition at the temperature and mixed with a stirrer to obtain a polymer, using a twin screw extruder Prepared by pellets.

Melting point of the stretch adhesive hot melt thermoplastic polyurethane resin prepared according to Example 5 is the same temperature as in Example 2 to 100 ℃ to about 110 ℃.

Example 6

Example 6 is another one of the specific examples of the thermoplastic polyurethane resin for the adhesive and hot melt for the adhesive layer, 69.53% by weight of butanediol / hexanediol adipate-based polyesterdiol (Poly Butanediol / Hexandiol Adipate) having a molecular weight of 2,500 To the stirrer, butyitol diol (1,4BG) 5.16% by weight, polysiloxane (Dimethyl Siloxane Hydroxyalkyl Terminated) is injected into 3.66% by weight after mixing all three compositions by stirring with a stirrer at 80 ℃ to maintain a liquid phase , 78.35% by weight of the mixed composition, 21.65% by weight of diphenylmethane diisocyanate (MDI) was added at about 60 ℃ to maintain a liquid phase to obtain a polymer, or all four compositions to form a liquid At the same time at a mixing ratio of the composition at the temperature and mixed with a stirrer to obtain a polymer, using a twin screw extruder It was prepared in the droplets (Pallet).

Melting point of the elastic adhesive hot-melt thermoplastic polyurethane resin prepared according to Example 6 is the same temperature as in Example 3 to 120 ℃ to 130 ℃.

Specific Examples 1 to 6 of the thermoplastic polyurethane resin for the adhesive and hot melt adhesive layer for excellent elasticity The composition ratio of the composition used in each of the two or more in the range of ± 2% by changing the elasticity and melting point is another A composition can be made.

Example 7

Example 7 is a specific example of a thermoplastic polyurethane resin excellent in elasticity and heat resistance for use as the protective layer, 74.16% by weight of a butanediol adipate-based polyesterdiol (Poly Butanediol Adipate) having a molecular weight of 2,500 Injected, butanediol (1,4BG) was injected 3.28% by weight, and 1.84% by weight of hydroquinone ethynol ether (HQEE), all three compositions were stirred and mixed with a stirrer at 95 ℃ to maintain a liquid phase Then, the mixed composition is maintained in the liquid phase, 20.71% by weight of diphenylmethane diisocyanate (MDI) is added at about 60 ℃ maintaining the liquid phase and mixed with a stirrer to obtain a polymer, or all four compositions are liquid At the same time, the mixture was added at the mixing ratio of the composition, mixed with a stirrer to obtain a polymer, and then pelleted using a twin screw extruder. allet).

The thermoplastic polyurethane resin prepared according to Example 7 having excellent elasticity and heat resistance has a relatively high heat resistance at a melting point of about 170 ° C. to 175 ° C.

Example 8

Example 8 is another one of the specific examples of the thermoplastic polyurethane resin having excellent elasticity and heat resistance for use as the protective layer, and 72.52% by weight of a butanediol adipate-based polyesterdiol having a molecular weight of 2,500 Inject to a stirrer, but 2.08% by weight of butanediol (1,4BG), and 4.68% by weight of hydroquinone ethynol ether (HQEE), all three compositions were stirred with a stirrer at 95 ℃ to maintain a liquid phase After mixing by mixing the composition to 79.29% by weight, while maintaining the liquid phase diphenylmethane diisocyanate (MDI) 20.71% by weight at about 60 ℃ maintaining the liquid phase, and then mixed with a stirrer Polymerization is obtained, or the four compositions are introduced at the same time as the composition ratio of the composition at the temperature of forming all of the liquid phase and mixed by stirring with a stirrer. After obtaining water, it was made into pellets using a twin screw extruder.

The thermoplastic polyurethane resin prepared according to Example 8 having excellent elasticity and heat resistance has a relatively high heat resistance at a melting point of about 180 ° C. to 185 ° C.

Example 9

Example 9 is another one of the specific examples of the thermoplastic polyurethane resin having excellent elasticity and heat resistance for use as the protective layer, 71.39% by weight of a butanediol adipate-based polyesterdiol (Poly Butanediol Adipate) having a molecular weight of 2,500 Injected into the stirrer, butanediol (1,4BG) is injected 1.26% by weight, and 6.63% by weight of hydroquinone ethynol ether (HQEE), all three compositions are stirred with a stirrer at 95 ℃ to maintain the liquid phase After mixing by mixing the composition to 79.29% by weight, while maintaining the liquid phase diphenylmethane diisocyanate (MDI) 20.71% by weight at about 60 ℃ maintaining the liquid phase and mixed with a stirrer to polymerize In order to obtain the polymerization, the four compositions were simultaneously injected at a temperature in which the composition ratios of the compositions were all liquid and mixed by stirring with a stirrer. After the obtained was prepared into a pellet (Pallet) using a twin-screw extruder.

The thermoplastic polyurethane resin prepared according to Example 9 having excellent elasticity and heat resistance has excellent heat resistance at a melting point of about 190 ° C to about 195 ° C.

Specific examples of the thermoplastic polyurethane resin having excellent elasticity and heat resistance Example 7 to Example 9 The composition ratio of the composition used in each can be changed by two or more in the range of ± 2% to make another composition having different elasticity and melting point .

Comparative Example 1

Comparative Example 1 is one of the specific comparative examples of the thermoplastic polyurethane resin for adhesives and hot melts for the adhesive layer, 72.64% by weight of a butanediol adipate-based polyesterdiol (Poly Butanediol Adipate) having a molecular weight of 1,000 was injected into a stirrer, butanediol ( 1,4BG) 0.5% by weight, pentanediol (NPG) 2.33% by weight and then all three compositions were stirred and mixed with a stirrer at 80 ℃ to maintain the liquid phase, and the composition is 75.47% by weight , 24.53% by weight of diphenylmethane diisocyanate (MDI) was added at about 60 ° C. to maintain a liquid phase, followed by mixing to obtain a polymer, or all four compositions were simultaneously added at a mixing ratio of the composition at a temperature at which a liquid phase was formed. After mixing with a stirrer to obtain a polymer, it was prepared as a pellet (Pallet) using a twin screw extruder.

Melting point of the adhesive hot-melt thermoplastic polyurethane resin prepared according to Comparative Example 1 is the same temperature as in Example 1 to about 70 ℃ to 80 ℃.

&Lt; Comparative Example 2 &

Comparative Example 2 is another of the specific comparative examples of the thermoplastic polyurethane resin for the adhesive and the hot melt for the adhesive layer, 72.77% by weight of a butanediol adipate-based polyesterdiol (Poly Butanediol Adipate) of molecular weight 1,000, butanediol (1,4BG ) Was injected at 1.25% by weight and pentanediol (NPG) at 1.45% by weight, and then all three compositions were stirred and mixed with a stirrer at 80 ° C. to maintain a liquid phase, and the composition was mixed with 75.47% by weight of diphenylmethane di 24.53% by weight of isocyanate (MDI) is added at about 60 ° C. to maintain a liquid phase and mixed to obtain a polymer, or all four compositions are simultaneously added at a mixing ratio of the composition at a temperature at which the liquid phase is mixed and mixed with a stirrer. After obtaining the polymer, it was prepared into pellets using a twin screw extruder.

Melting point of the adhesive hot-melt thermoplastic polyurethane resin prepared according to Comparative Example 2 is the same temperature as in Example 2 to about 100 ℃ to 110 ℃.

&Lt; Comparative Example 3 &

Comparative Example 3 is another of the specific comparative examples of the thermoplastic polyurethane resin for the adhesive and the hot melt for the adhesive layer, 72.9% by weight of a butanediol adipate-based polyesterdiol (Poly Butanediol Adipate) having a molecular weight of 1,000, butanediol (1,4BG ) Is injected at 2.0% by weight and 0.58% by weight of pentanediol (NPG), and then all three compositions are stirred and mixed with a stirrer at 80 ° C. to maintain a liquid phase, and the composition is 75.47% by weight of diphenylmethane di 24.53% by weight of isocyanate (MDI) is added at about 60 ° C. to maintain a liquid phase and mixed to obtain a polymer, or all four compositions are simultaneously added at a mixing ratio of the composition at a temperature at which the liquid phase is mixed and mixed with a stirrer. After obtaining the polymer, it was prepared into pellets using a twin screw extruder.

Melting point of the adhesive hot-melt thermoplastic polyurethane resin prepared according to Comparative Example 3 is 120 to about 130 is the same temperature as in Example 3.

&Lt; Comparative Example 4 &

Comparative Example 4 is one of the specific comparative examples of the thermoplastic polyurethane resin having excellent elasticity and heat resistance for use as a protective layer, 64.8% by weight of butanediol adipate-based polyesterdiol (Poly Butanediol Adipate) having a molecular weight of 1,000, butanediol (1 , 4BG) and 2.6% by weight of hydroquinone ethynol ether (HQEE) were injected, and all three compositions were stirred and mixed with a stirrer at 95 ° C. to maintain liquid phase, and then the mixed composition was 71.3% by weight. After distilling the composition into a liquid state, diphenylmethane diisocyanate (MDI) was injected at 28.degree. C. while maintaining 28.7% by weight of diphenylmethane diisocyanate (MDI), and then mixed with a stirrer to obtain a polymer. At the same time, the mixture was injected at the same temperature at the rate of forming the liquid phase and mixed by stirring with a stirrer to obtain a polymer, and then pelleted using a twin screw extruder. It was prepared in (Pallet).

The thermoplastic polyurethane resin having excellent heat resistance according to Comparative Example 4 has a melting point of about 170 ° C. to 175 ° C., which is the same as that of Example 7.

<Example 10 to Example 15>

Examples 10 to 15 is a stretch adhesive hot melt polyurethane poly prepared in the first invention Examples 1 to 6 in order to produce a laminated film by laminating a stretch adhesive hot melt polyurethane film of the third invention and the prepared film The urethane resin was manufactured as a T-Die film with a thickness of 200 μm using a single screw extruder and a flat die.

<Examples 16 to 18>

Embodiment 16 to Example 18 is a single screw extruded thermoplastic elastomer resin having a stretch and heat resistance prepared in Examples 7 to 9 of the second invention in order to manufacture the laminated film of the third invention (Single Screw) Using an extruder and a flat die, a T-Die film having a thickness of 110 μm was manufactured.

<Examples 19 to 24>

Examples 19 to 24 are prepared by using a single screw extruder and a flat die for the stretchable hot melt thermoplastic polyurethane resin prepared in Examples 1 to 6 of the first invention. Thickness of 200 탆 T-Die film and the thermoplastic polyurethane resin having elasticity and heat resistance prepared in Examples 7 to 9 of the second invention and a single screw extruder 110-thick T-Die films (T-Die) films prepared by using a flat die are laminated to maintain a predetermined time by applying a constant pressure (heat and pressure) at a predetermined temperature.

<Comparative Example 5 to Comparative Example 7>

Comparative Example 5 to Comparative Example 7 is a single screw extruder and a flat die by using a hot-melt thermoplastic polyurethane resin prepared in Comparative Examples 1 to 3 to compare the characteristics in correspondence with the first invention. It was prepared as a 200㎛ T-Die film using.

Comparative Example 8

Comparative Example 8 uses a single screw extruder and a flat die to form a thermoplastic polyurethane resin prepared in Comparative Example 4 in order to correspond to the second invention. It is manufactured from a (T-Die) film.

<Comparative Example 9 to Comparative Example 11>

Comparative Example 9 to Comparative Example 11 were prepared using the film prepared in Comparative Example 5 to Comparative Example 7 and the film prepared in Comparative Example 8 for comparison with the laminated film prepared in Examples 19 to 24 above. A laminated film was prepared in the same manner as in Example 19 to Example 24.

A laminated film obtained by laminating a stretchable hot melt thermoplastic polyurethane film prepared according to Examples 10 to 15 and a thermoplastic polyurethane film having elasticity and heat resistance for a protective layer prepared according to Examples 16 to 18. To prepare a flexible adhesive hot melt thermoplastic polyurethane film prepared according to Example 10 and the thermoplastic polyurethane film having a stretch and heat resistance for the protective layer prepared according to Examples 16 to 18, respectively, By producing a laminated film having different melting points of the adhesive layer and different heat resistances of the protective layer, users can select and use them according to their needs.

That is, the elastic adhesive hot melt thermoplastic polyurethane film prepared according to Example 10 and the thermoplastic polyurethane film having elasticity and heat resistance for the protective layer prepared according to Examples 16 to 18, respectively, are laminated to The melting point is high and the heat resistance different from each other to produce a laminated film to be used according to the required use, or to prepare a thermoplastic polyurethane film having a stretch and heat resistance for the protective layer prepared according to Example 16 and Examples 10 to By laminating the stretchable hot melt thermoplastic polyurethane resin films prepared in Example 15, respectively, the melting points of the adhesive layers may be different from each other, and the same heat resistance may be prepared to be selectively used according to the required use.

The stretchable hot melt thermoplastic polyurethane resin film prepared according to Examples 10 to 15 and the thermoplastic polyurethane resin film having elasticity and heat resistance for the protective layer prepared according to Examples 16 to 18 as described above. When the laminated film is manufactured by laminating and applying a constant temperature heat and a constant pressure, the laminated film having various characteristics as described above is produced, and selected and used according to a suitable use considering the melting point of the adhesive layer and the heat resistance of the protective layer. Therefore, damage, shrinkage and deformation of the fabric can be prevented.

It looks at in detail with respect to the manufacturing method of the laminated film according to the present invention. In the manufacturing method of the laminated film, 60% to 85% by weight of a polyol having a molecular weight of 1500 to 2500 is injected, 5% to 10% by weight of a bifunctional chain extender is injected, and 35% by weight of organic diisocyanate to It is prepared by injecting and mixing 5% by weight, and the polyol, the bifunctional chain extender and the organic diisocyanate react with each other to bond the adhesive and the adhesive layer with a stretchable hot melt thermoplastic polyurethane resin having a melting point of 80 ° C to 140 ° C. Through the process of preparing the film, 60 to 85% by weight of a polyol having a molecular weight of 1500 to 2500 is injected, 5 to 10% by weight of the difunctional chain extender is mixed, and organic diisocyanate is injected. It is prepared by injecting and mixing 35% by weight to 5% by weight, and the melting point of the polyol, the bifunctional chain extender and the organic diisocyanate reacted with each other is 160 ° C. to Through the process of producing a protective layer film from thermoplastic polyurethane resin having a stretch and heat resistance having a temperature of 230 ℃, the adhesive layer film made of a predetermined thickness of the hot-melt thermoplastic polyurethane resin and the thermoplastic poly with the elasticity and heat resistance It is made of a process of laminating a protective layer film made of a urethane resin to a certain thickness to maintain a certain time at a constant pressure and temperature to bond.

Polyols, polyester diols, diisocyanates, and the like used in the process of preparing the adhesive film and the adhesive layer film from the stretchable hot melt thermoplastic polyurethane resin and the process of preparing the protective layer film from the thermoplastic polyurethane resin having elasticity and heat resistance. The bifunctional chain extender is the same as described in the above-mentioned composition of the flexible adhesive hot melt thermoplastic polyurethane resin, so it is omitted to avoid overlapping substrates.

In the process of preparing the adhesive film and the adhesive layer film from the stretch adhesive hot melt thermoplastic polyurethane resin and the process of manufacturing the protective layer film from the thermoplastic polyurethane resin having heat resistance and elasticity, the film of the adhesive layer is a stretch adhesive Hot-melt polyurethane resin is formed 50㎛ to 2,000㎛ thickness, the protective film is a thermoplastic polyurethane resin excellent in elasticity and heat resistance is preferably formed to a thickness of 30㎛ to 2,000㎛, it may be formed to a value out of this have.

Melting points produced according to the process of the manufacturing method of the laminated film are different from each other and the laminated film having excellent heat resistance also belongs to the protection scope of the present invention.

Melting point, specific gravity, 100% modulus, tensile strength, elongation rate, tear strength and adhesive force of the stretchable hot melt thermoplastic polyurethane film of Examples 10 to 15 prepared according to the present invention were measured, and Examples 16 to 16 were carried out. Melting point, specific gravity, hardness, 100% modulus, tensile strength, elongation rate, tear strength, light resistance, and melt index of the thermoplastic polyurethane film having the elasticity and heat resistance of Example 18 were measured, and were laminated in Examples 19 to 24. The adhesive strength and the thickness of the protective layer after the adhesion of the fabric and the laminated film was measured.

The melting point of the elastic adhesive hot melt thermoplastic polyurethane resin prepared above and the thermoplastic polyurethane resin having elasticity and heat resistance was measured according to the method specified in ASTM D 3835, and the flow starting temperature was measured. 3 to Table 4 are shown.

Specific gravity was measured by the submerged method according to the method specified in ASTM D 792, the results are shown in Table 3 to Table 4.

The hardness was measured by using Shore hardness tester type A according to the method specified in ASTM D 2240 to measure the hardness in the initial compression state, the results are shown in Table 3 to Table 4.

100% modulus, tensile strength and elongation (%) were measured using a 200kg universal tester according to the method specified in ASTM D 412, and the results are shown in Tables 3 and 4. However, the specimen was a dumbbell No. 3 type and the tensile speed was set to 500m / min.

The tear strength was measured using a 200kg universal testing machine according to the method specified in ASTM D 624, and the results are shown in Tables 3 and 4. However, the tear speed was 500 m / min.

The measurement of the light fastness was measured using a Q-UV Weather-O-meter, an accelerated light resistance tester, to measure the color difference of the sample, and the color difference was measured by the method specified in JIS L 0805. The results are shown in Tables 3 to 4.

The Q-WEB Weather-O-Meter is light from an FS-40 fluorescent solar lamp, which ranges from 280 nm to 350 nm in the ultraviolet wavelength range. The lamp capacity was 40W * 8, 102V (0.43A), the distance from the sample was fixed at 50 mm, and the temperature of the specimen surface was tested for 24 hours under 40 ° C.

The melt index was measured using a load of 2.16 kg, a preheating time of 7 minutes, a temperature of 195 ° C, and a die of 1 × 10 mm according to the method specified in ASTM D 1238. The results are shown in Tables 3 and 4. Indicated.

In the case of measuring the adhesive strength, the hot melt thermoplastic polyurethane resin film for elastic bonding was press-bonded at the temperatures shown in Table 1 in the order of artificial leather, hot melt polyurethane film, and mesh fabric, and the hot melt thermoplastic polyurethane resin film for elastic bonding and elasticity And laminated film of thermoplastic polyurethane film having heat resistance, press-bonded laminated film to each of artificial leather, mesh fabric and polyester fabric at the temperature as shown in Table 2 in accordance with the method specified in ASTM D 1876. Measured using a 200kg universal testing machine, the results are shown in Table 5. However, the speed was 200 m / min.

1 is a film of a stretch adhesive hot melt thermoplastic polyurethane resin prepared according to Examples 1 to 6 of the present invention according to Examples 10 to 15 in a synthetic leather and a mesh fabric at a predetermined temperature, pressure and time It is a photograph that measures the adhesive strength by giving a bond.

Figure 2 is a photograph taken with an electron microscope (Micro Scope) to 300 times the magnification of the laminated film with elasticity and heat resistance prepared according to Example 19 of the present invention.

Figure 3 is a 300 times the thickness of the protective layer of the laminated film prepared by laminating a laminate film prepared in accordance with the stretch and heat resistance according to Examples 19 to 24 of the present invention given a predetermined temperature, pressure and time. This is a magnified picture taken with an electron microscope.

The laminated film is manufactured by using a hot-melt thermoplastic polyurethane resin film having different melting points according to Examples 1 to 6 and a thermoplastic polyurethane resin film having heat resistance prepared according to Examples 7 to 14. In this case, 18 laminated films having different characteristics of the adhesive layer and the protective layer were prepared, and the 18 laminated films were photographed with an electron microscope. However, the remaining pictures are shown in FIGS. 3 and 3 to 5. Since it is predictable through the contents set forth in, it is omitted to attach to the drawings on the specification of the present invention.

Table 1 shows the temperature, pressure and time during the adhesion of the adhesive hot melt thermoplastic polyurethane film and the artificial leather, hot melt polyurethane film and the mesh fabric. The above-mentioned laminated film is given to give a specific temperature, pressure and time to give a specific content, and ± 10 or so in these numerical ranges can be changed.

Table 2 shows the temperature, pressure and time of adhesion of the laminated film and the artificial leather, mesh fabric and polyester fabric.

The thickness of the protective layer was measured using an electron microscope (Micro Scope), and the results are shown in FIG. 3. However, the magnification was 300 times.

Table 3 shows the experimental data for the adhesive hot melt thermoplastic polyurethane film prepared in Examples 10 to 15.

Table 4 shows experimental data for the heat resistant thermoplastic polyurethane film prepared according to Examples 16 to 18.

Table 5 shows the experimental data for the laminated film of the adhesive hot-melt thermoplastic polyurethane and heat-resistant thermoplastic polyurethane prepared by Examples 19 to 24.

As can be seen through various embodiments and comparative examples according to the present invention, the 100% modulus of the produced film is 30kgf / ㎠ or less in the present invention, the comparative example is larger than 30kgf / ㎠, the elongation exhibiting elasticity is It can be seen that the present invention is 650% or more, and the comparative example is smaller than 650%. That is, it can be seen that both the film and the laminated film according to the present invention have excellent elasticity.

According to the present invention, the polyol, the bifunctional chain extender, and the organic diisocyanate are mixed and reacted at a predetermined weight percent ratio to adjust the melting point to adjust the melting point of the hot melt polyurethane adhesive resin having different melting points. The adhesive strength is maintained by manufacturing the film, and it protects against shrinkage, deformation and discoloration of the fabric, which is the adherend according to the processing conditions, and heat-bonds and sticks by laminating it with a protective layer made of thermoplastic polyurethane resin having excellent elasticity and heat resistance. ), By protecting the fabric, the appearance is beautiful and can be prevented from leaking along the sewing line.

In addition, it does not use VOC (Volatile Organic Compounds) compared to solvent type polyurethane, so it can reduce environmental pollution, and it is possible to recycle the burrs or product scraps generated during film manufacturing, resulting in higher production efficiency. It is possible to greatly reduce the production cost and to adjust the melting point hot melt thermoplastic polyurethane that can adjust the melting point to maintain the chemical properties with good chemical resistance, cold resistance, and water resistance, and to use an adhesive film and a thermoplastic polyurethane resin having excellent elasticity and heat resistance. The laminated film serving as a protective layer can be usefully used for the manufacture of shoes, sports shoes, leisure clothing, and various automotive applications (eg, automotive interior adhesives).

Based on the various embodiments and experiments, the film made of the elastic adhesive hot melt thermoplastic polyurethane resin according to the present invention preferably has a 100% modulus of 10 kgf / cm 2 to 30 kgf / cm 2 and an elongation of 650 to 1,200%. The physical properties of the film made of thermoplastic polyurethane resin having elasticity and heat resistance are preferably 100% modulus of 10 kgf / cm 2 to 30 kgf / cm 2 and an elongation of 650 to 1,200%.

The laminated film in which the two films are laminated has a melting point of the adhesive layer between 80 ° C. and 140 ° C., and a melting point of the protective layer between 160 ° C. and 230 ° C., and the laminated film has a 100% modulus of 10 kgf / cm 2 to 30 kgf / cm 2. And the elongation is preferably between 650 and 1,200%.

The present invention is to prevent the damage, shrinkage, deformation, etc. of the fabric caused by the heat generated during the adhesion in order to be able to select and use the laminated film having the adhesive and the adhesive layer according to the characteristics of the fabric, polyol of the liquid sand, to improve the elasticity, Injection-mixing of bifunctional chain extender and organic diisocyanate to prepare and mix elastic adhesive hotmelt thermoplastic polyurethane resin having various melting points between 80 ° C and 140 ° C, polyol, bifunctional chain extender and organic diisocyanate. It is possible to provide a thermoplastic polyurethane resin having elasticity and heat resistance having a melting point of 160 ° C to 230 ° C and a thermoplastic polyurethane laminated film having excellent heat resistance and elasticity by laminating a film made using the resin. This is very high.

Claims (30)

In the process of preparing a stretch adhesive hot melt thermoplastic polyurethane resin, 60 to 85 wt% of a polyol having a molecular weight of 1500 to 2500 is injected, and a difunctional chain extender is mixed to inject 5 to 10 wt%. It is prepared by injecting and mixing 35% by weight to 5% by weight of organic diisocyanate, and the melting point of the polyol, the bifunctional chain extender and the organic diisocyanate reacted with each other is 80 to 140 ℃, elongation rate is Hot melt thermoplastic polyurethane resin for stretch bonding between 650% and 1,200%. The method according to claim 1,
The polyol may be selected from polyester diols, polyether diols, and polycarbonate diols, or a flexible adhesive hot melt having a melting point of 65 ° C. to 140 ° C. composed of a mixture of two or more of them. Thermoplastic polyurethane resin. The method according to claim 2,
The polyester diol is composed of lactone-based polyester diols and adipic acid-based diols, or a flexible adhesive hot-melt thermoplastic polyurethane resin having a melting point of 65 ° C. to 140 ° C. composed of polyester diols or adipic acid-based polyester diols. . The method according to claim 1,
The diisocyanate is a stretch adhesive hot melt thermoplastic polyurethane resin having a melting point of 80 ° C to 140 ° C selected from either one of aromatic isocyanates and aliphatic isocyanates or a mixture of two or more of them. The method of claim 4,
The diisocyanate may be selected from any one of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, or may have a melting point of 80 ° C. or less in a mixture of two or more thereof selected and mixed. Stretch adhesive hot melt thermoplastic polyurethane resin with 140 ℃. The method according to claim 1,
The difunctional chain extender is a diol-based ethylene glycol, diethylene glycol, butanediol, hexanediol, neopentyl glycol, dimethylcyclonucleic acid dimethinol, polytetramethylene ether glycol, hydroquinone ethynol ether, methylene pentane diol Melting point of 80 ° C to 140 ° C, which is selected from trimethylolpropane and modified polysiloxane glycol-based dimethyl siloxane hydrooxyalkyl terminators, or a mixture of two or more of them. Stretch adhesive hot melt thermoplastic polyurethane resin with. 60% to 85% by weight of a polyol having a molecular weight of 1500 to 2500 is injected, and either 5% by weight or 10% by weight of a bifunctional chain extender is selected or mixed. It is prepared by injecting and mixing 35% by weight to 5% by weight of diisocyanate, and 100% modulus of elastic adhesive hot melt thermoplastic polyurethane film has a modulus of 10 kgf / cm 2 to 30 kgf / cm 2 and elongation is 650% to 1,200%. And a hot melt thermoplastic polyurethane film for elastic bonding having a melting point of 80 ° C to 140 ° C. The method of claim 7,
The polyester diol used in the process of manufacturing a film from the stretch adhesive hot melt thermoplastic polyurethane resin is selected from lactone polyester diol or adipic acid polyester diol, or two or more thereof are selected. A stretchable hot melt adhesive thermoplastic polyurethane film having a melting point of 80 ° C. to 140 ° C. composed of a mixed mixture. The method according to claim 8,
The polyester diol used in the process of manufacturing the film from the stretch adhesive hot melt thermoplastic polyurethane resin is composed of lactone polyester diol or adipic acid polyester diol or lactone polyester diol and adipic acid polyester diol. Stretch adhesive hot melt thermoplastic polyurethane film having a melting point of 80 ℃ to 140 ℃. The method of claim 7,
The diisocyanate used in the process for producing a film from the stretch adhesive hot melt thermoplastic polyurethane resin may be selected from one of aromatic isocyanates and aliphatic isocyanates, or may be a melting point formed of a mixture of two or more of them. Stretch adhesive hot melt thermoplastic polyurethane film having a temperature of 80 ° C to 140 ° C. The method of claim 10,
The diisocyanate used in the process for producing a film from the stretch adhesive hot melt thermoplastic polyurethane resin is selected from any one of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate or these A thermoplastic polyurethane film for stretchable hot melt adhesive having a melting point of 80 ° C to 140 ° C, composed of a mixture of two or more of them. The method of claim 7,
The bifunctional chain extender used in the process of manufacturing a film from the stretch adhesive hot melt thermoplastic polyurethane resin is a diol-based ethylene glycol, diethylene glycol, butanediol, hexanediol, neopentyl glycol, dimethylcyclonucleic acid dimethy Selected from among knol, polytetramethylene ether glycol, hydroquinone ethynol ether, methylene pentane diol, triol-based trimethylolpropane and modified polysiloxane glycol-based dimethyl siloxane hydrooxyalkyl terminator or two of them. A flexible adhesive hot melt thermoplastic polyurethane film having a melting point of 80 ° C. to 140 ° C. composed of a mixture of several or more selected mixtures.       Inject 60% to 85% by weight of a polyol having a molecular weight of 1500 to 2500, mix 5% to 10% by weight of a bifunctional chain extender, and 35% to 5% by weight of an organic diisocyanate. It is prepared by injection mixing, the polyol, the bifunctional chain extender and the organic diisocyanate prepared by reacting with each other, the melting point is 160 ℃ to 230 ℃, elongation and elasticity and heat resistance of between 650% to 1,200% Thermoplastic polyurethane resin. The method according to claim 13,
The polyol may be selected from polyester diols, polyether diols, and polycarbon diols, or may have elasticity and heat resistance having a melting point of 160 ° C to 230 ° C as a mixture of two or more of them. Thermoplastic polyurethane resin provided. The method according to claim 14,
The polyester diol may be composed of lactone-based polyester diols or adipic acid-based polyester diols, or may have elasticity and heat resistance having a melting point of 160 ° C. to 230 ° C., composed of lactone-based polyester diols and adipic acid-based polyester diols. Thermoplastic polyurethane resin. The method according to claim 13,
The diisocyanate is a thermoplastic polyurethane resin having elasticity and heat resistance having a melting point of 160 ° C. to 230 ° C., which is selected by using any one of aromatic isocyanates and aliphatic isocyanates or a mixture of two or more of them. . 18. The method of claim 16,
The diisocyanate may be selected from any one of diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate, or may have a melting point of 160 or more selected from these mixtures. Thermoplastic polyurethane resin with elasticity and heat resistance between ℃ and 230 ℃. The method according to claim 13,
The difunctional chain extender is a diol-based ethylene glycol, diethylene glycol, butanediol, hexanediol, neopentyl glycol, dimethylcyclonucleic acid dimethinol, polytetramethylene ether glycol, hydroquinone ethynol ether, methylene pentane diol And a thermoplastic polyurethane resin having elasticity and heat resistance having a melting point of 160 ° C. to 230 ° C., selected from any one of trimethylol propane of a triol series, or a mixture of two or more of them. Inject 60% to 85% by weight of a polyol having a molecular weight of 1500 to 2500, mix 5% to 10% by weight of a bifunctional chain extender, and 35% to 5% by weight of an organic diisocyanate. It is prepared by injection mixing, and the thermoplastic polyurethane film physical properties of the mixed prepared 100% modulus of 10kgf / ㎠ to 30kgf / ㎠, elongation is between 650 to 1,200%, the melting point of 160 ℃ to 230 ℃ stretch and heat resistance Thermoplastic polyurethane film provided. The method of claim 19,
The polyol used in the process for producing a film from the thermoplastic polyurethane resin having elasticity and heat resistance may be selected from polyester diols, polyether diols, and polycarbonate diols, or two or more thereof. A thermoplastic polyurethane film having elasticity and heat resistance having a melting point of 160 ° C. to 230 ° C. formed of a mixed mixture. The method of claim 19,
The polyester diol used in the process for producing a film from the thermoplastic polyurethane resin having the elasticity and heat resistance is composed of lactone polyester diol or adipic acid polyester diol or lactone polyester diol or adipic acid polyester. A thermoplastic polyurethane film having elasticity and heat resistance having a melting point of 160 ° C. to 230 ° C. made of diol. The method of claim 19,
The diisocyanate used in the process for producing a film from the thermoplastic polyurethane resin having elasticity and heat resistance may be selected from an aromatic isocyanate and an aliphatic isocyanate, or may be selected from a mixture of two or more thereof. A thermoplastic polyurethane film having elasticity and heat resistance having a melting point of 160 ° C to 230 ° C. 23. The method of claim 22,
The diisocyanate used in the process for producing a film from the thermoplastic polyurethane resin having the elasticity and the heat resistance may be selected from diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, or Or a thermoplastic polyurethane film having elasticity and heat resistance having a melting point of 160 ° C. to 230 ° C. composed of a mixture of two or more of these selected and mixed. The method of claim 19,
The bifunctional chain extender used in the process for producing a film from the thermoplastic polyurethane resin having elasticity and heat resistance is ethylene glycol, diethylene glycol, butanediol, hexanediol, neopentyl glycol, and dimethylcyclonucleic acid based on diols. Melting point composed of a mixture of dimethinol, polytetramethylene ether glycol, hydroquinone ethynol ether, methylene pentane diol, and triol-based trimethylol propane, or a mixture of two or more of them selected The thermoplastic polyurethane film which has the elasticity and heat resistance which are 160 degreeC-230 degreeC. In the laminated film manufacturing method,
60 wt% to 85 wt% of a polyol having a molecular weight of 1500 to 2500 is injected, 2 wt% to 10 wt% of a difunctional chain extender is mixed, and 35 wt% to 5 organic diisocyanate is injected. It is prepared by injecting and mixing by weight, and the polyol, the bifunctional chain extender and the organic diisocyanate react with each other to bond the adhesive layer and the adhesive layer film with a stretchable hot melt thermoplastic polyurethane resin having a melting point of 80 ° C to 140 ° C. Manufacturing a process;
Inject 60% to 85% by weight of a polyol having a molecular weight of 1500 to 2500, mix 5% to 10% by weight of a bifunctional chain extender, and 35% to 5% by weight of an organic diisocyanate. It is prepared by injection mixing, and the protective layer film is made of a thermoplastic polyurethane resin having elasticity and heat resistance having a melting point of 160 ℃ to 230 ℃ prepared by reacting the polyol, difunctional chain extender and organic diisocyanate reacted with each other Process of doing; And
Laminating the adhesive layer film of the elastic adhesive hot melt thermoplastic polyurethane resin prepared above and the protective layer film of the thermoplastic polyurethane resin including the prepared elasticity and heat resistance, and maintaining the adhesive layer at a predetermined pressure and temperature for a predetermined time. But
The thermoplastic polyurethane film produced by the above process has a 100% modulus of 10 kgf / cm 2 to 30 kgf / cm 2, an elongation of 650 to 1,200%, a melting point of the adhesive layer having a melting point of 80 ° C. to 140 ° C., and a melting point of the protective layer. Laminated film production method between 160 ℃ to 230 ℃. The method according to claim 25, wherein the melting point of the adhesive layer produced by the laminated film manufacturing method is 80 ℃ to 140 ℃, the melting layer of the protective layer is 160 ℃ to 230 ℃, the laminated film properties of 100% modulus of 10kgf / A laminated film having a cm 2 to 30 kgf / cm 2 and an elongation of between 650 and 1,200%. 27. The method of claim 26,
The laminated film is a stretch adhesive hot melt polyurethane resin which is a film of an adhesive layer is formed to a thickness of 50 micrometers to 2000 micrometers,
The film of the protective layer is a thermoplastic polyurethane resin having excellent elasticity and heat resistance, and has a melting point of 80 ° C. to 140 ° C. and a melting point of the protection layer of 160 ° C. to 230 ° C. Saiin laminated film. Inject 35% to 75% by weight of a liquid polyol having a molecular weight of 500 to 3,000, inject 5% to 15% by weight of two kinds of bifunctional chain extenders, and add 60 parts of a liquid organic diisocyanate. It is prepared by injecting and mixing by weight to 10% by weight, and the polyol, the bifunctional chain extender and the organic diisocyanate react with each other to bond the elastic adhesive hot melt thermoplastic polyurethane resin having a melting point of 60 ℃ to 140 ℃ And adhesive layer films,
35 wt% to 75 wt% of a liquid polyol having a molecular weight of 500 to 3000 is injected onto the adhesive and adhesive layer film with the elastic adhesive hot melt thermoplastic polyurethane resin prepared above, and 5 weight by mixing a bifunctional chain extender. It is prepared by injecting from 60% to 10% by weight of a liquid organic diisocyanate by injecting% to 15% by weight, and the melting point of the polyol, the bifunctional chain extender and the organic diisocyanate reacted and bonded to each other. After laminating a protective layer film made of a thermoplastic polyurethane resin having elasticity and heat resistance between 160 ° C. and 230 ° C., and bonding it under heat and pressure, the melting point of the adhesive layer is between 65 ° C. and 140 ° C. and the heat resistance of the protective layer is Laminated film between 160 ℃ to 230 ℃. 29. The method of claim 28,
The laminated film is formed of a stretch adhesive hot melt polyurethane resin, which is a film of an adhesive layer, having a thickness of 50 micrometers to 1000 micrometers,
The film of the protective layer is a thermoplastic polyurethane resin having excellent elasticity and heat resistance, and is formed at a thickness of 30 to 2000 micrometers, and has a melting point of 65 ° C. to 140 ° C., and the heat resistance of the protective layer is 160 ° C. to 230 ° C. Saiin laminated film. The method according to claim 28 or 29,
The laminated film has a melting point of the adhesive layer is 65 ℃ to 140 ℃, the heat resistance of the protective layer is 160 ℃ to 230 ℃, the laminated film with elasticity and heat resistance is 100% modulus of 30kgf / ㎠ to 10kgf / ㎠ , Laminated film with elongation between 650% and 1,000%.

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