KR20170077891A - Hot Melt Adhesive Film Having Excellent Adhesion And Flexibility - Google Patents

Abstract

The present invention provides a polyurethane coating composite comprising a substrate layer and a hot-melt adhesive film layer composed of a polyether ester-based elastomer resin (PTEE) formed on the upper surface of the substrate layer and a polyurethane coating layer formed on the upper surface of the adhesive film layer, The hot-melt adhesive film preferably has an intrinsic viscosity (IV) of 1.0 to 1.8, a melting point (MP) of 80 to 160 ° C, a flex resistance of 30,000 or more, and an adhesive strength of 4.0 kgf / in or more to a water- To provide a hot-melt adhesive film excellent in bending resistance and adhesive strength.

Description

[0002] Hot Melt Adhesive Film Having Excellent Adhesion And Flexibility [

The present invention relates to a hot-melt adhesive film excellent in bending resistance and adhesive strength, and more particularly to a hot-melt adhesive film excellent in bending resistance and adhesive strength using a hot-melt adhesive film using a polyether ester-based elastomer resin (TPEE) will be.

In general, when shoes are manufactured, artificial leather is used rather than using expensive natural leather as a whole. Such artificial leather includes wet type polyurethane artificial leather and dry type polyurethane artificial leather. These artificial leathers are used to produce finished shoes through cutting and sewing processes, or in the case of polyurethane artificial leathers using SPANDEX, which has excellent stretchability, by injection of foam (FOAM). .

Accordingly, various methods have been proposed for producing artificial leather having excellent commercial properties as described above. For example, Korean Patent Registration No. 10-0344110 discloses a polyurethane artificial leather and a manufacturing method thereof, In the method for producing synthetic leather fabrics of Patent Document No. 2004-0013631 and the method for producing polyurethane synthetic leather using the fabric produced by this method, a staple fiber having a fineness of 1.0 to 4.0 denier and a fiber length of 30 to 76 mm is carded ) Discloses a synthetic leather fabric manufacturing method in which a web is manufactured, crosslapping, and then the web is knitted by needle punching with a polar fleece.

As described above, the fabric used for the synthetic leather is mainly a nonwoven fabric, and the nonwoven fabric is manufactured by cutting a staple fiber having a fineness of 1.0 to 1.3 denier, a fiber length of 38 to 76 mm and nylon, The web is manufactured by cross-lapping it to an appropriate weight, and then the web is bound by needle punching at a needle punching machine at a needle density of 1,000 to 1,500 times / cm 2, and a post-processing step such as a calendering step and a heat shrinking step is added It is.

 Also, a large number of adhesives for bonding the polyurethane coating layer and the fabric have been proposed. For example, adhesives for polyester fibers of Korean Patent Registration No. 10-0302108 and low-melting-point polyester fibers of Korea Patent Application No. 2006-0136158 A hot melt adhesive film having a multilayer structure of Korean Patent Registration No. 10-1098885, and a hot melt adhesive film composition and hot melt adhesive film for shoe insole of Korean Patent Application No. 2007-0055515.

However, the polyurethane synthetic leather produced by using the conventional nonwoven fabric as the raw material of the synthetic leather as described above is excellent in various physical properties such as tensile strength and tactility, but is hard and not good in cushioning, It has a disadvantage that it is difficult to use it as a material for shoes or the like alone.

Therefore, in order to produce artificial leather having excellent physical properties that can be used for various purposes, that is, an artificial leather excellent in flexibility suitable for the use of shoes, it is necessary to develop a material capable of increasing the formability of synthetic leather and imparting cushioning.

In addition, there is a demand for a product that can improve the productivity and workability by eliminating the sewing process so that shoes can be manufactured without using the artificial leather used as a material for manufacturing shoes by using the non-sewing bonding method.

In order to solve the above-mentioned problems, the present invention can increase the formability of synthetic leather, provide cushion and flexibility, and use a non-sewn bonding method, thereby improving productivity and workability A hot-melt adhesive film having a heat-sealable property.

In order to solve the above problems, the present invention provides a hot melt adhesive film comprising a substrate layer and a polyether ester-based elastomer resin (PTEE) formed on the upper surface of the substrate layer, and a polyurethane coating layer formed on the upper surface of the adhesive film layer Wherein the hot melt adhesive film has an intrinsic viscosity (IV) of 1.0 to 1.8, a melting point (MP) of 80 to 160 DEG C, a flex resistance of 30,000 or more times, and an adhesive strength to a water- Wherein the hot-melt adhesive film has a cold-proof property and an excellent adhesive force.

In the present invention, the polyetherester elastomer resin is obtained by esterifying a diol (diol) and a dicarbonic acid as raw materials of a hard segment and polycondensation of a polyol as a soft segment raw material, The diol may be a mixture of at least one of ethylene glycol, butylene glycol and polytetramethylene glycol, and the dicarbonic acid may be a mixture of dimethyl terephthalate (DMT) or dimethyl isophthalate (DMI) (PTMG), polyethylene glycol (PEG), and poly (tetramethylene ether) glycol. The polyol may be a mixture of one or more of the above- Propylene glycol (PPG). The hot melt adhesive has excellent cold resistance and excellent adhesive strength. It provides the film.

The present invention also relates to an anhydride resin, wherein the anhydride resin is selected from the group consisting of methyltetrahydrophthalic anhydride (MeTHPA), methylhexahydrophthalic anhydride (MeHHPA), terahydophthalic anhydride (THPA) And a ropthalic anhydride (HHPA). The hot melt adhesive film is excellent in cold and cold bending properties and adhesive strength.

The present invention also relates to a process for preparing the conjugated diene-conjugated diene-anhydride resin by reacting a conjugated diene having two double bonds with a maleic anhydride in a Diels-Alder reaction The present invention provides a hot-melt adhesive film excellent in low-temperature bending resistance and adhesive strength.

Also, the present invention provides a hot-melt adhesive film having a low molecular weight of 400 to 20,000 and a polyether ester-based resin content of 10 to 80% by weight.

The present invention also provides a non-woven form shoe using the hot-melt adhesive film.

The present invention can be used as a hot melt adhesive film having heat-fusible properties and a non-bar type polyurethane artificial leather using the same. In the case of producing a finished article of shoes using artificial leather, productivity and productivity are improved because cutting and sewing are not performed.

In addition, unlike conventional products, the present invention is excellent in adhesion to a water-repellent fabric and can maintain a soft and bulky cushioning property even after heat bonding, and thus can be applied to various applications. Effect.

Further, the present invention simplifies the conventional multi-layer structure, and is characterized in that it can provide excellent molding property when producing products such as various patterns or elaborate patterns.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view of a hot-melt adhesive film excellent in low-temperature bending resistance and adhesive force of a rod-like material according to a preferred embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted so as to avoid obscuring the subject matter of the present invention.

As used herein, the terms "substantially", "substantially", and the like are used herein to refer to a value in or near the numerical value when presenting manufacturing and material tolerances inherent in the meanings mentioned, Absolute numbers are used to prevent unauthorized exploitation by unauthorized intruders of the mentioned disclosure

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane coating composite (100), comprising: a substrate layer (110); A hot-melt adhesive film layer 120 made of a polyether ester-based elastomer resin formed on the upper surface of the substrate layer, and a polyurethane coating layer 130 formed on the upper surface of the adhesive film layer.

1 is a cross-sectional view of a rod-like polyurethane coating composite 100 according to a preferred embodiment of the present invention, wherein the hot-melt adhesive film layer is made of a polyether ester-based elastomer resin.

The polyetherester elastomer resin is obtained by esterifying a diol and a dicarbonic acid as a raw material of a hard segment and polycondensation of a polyol as a soft segment raw material,

The diol may be composed of a mixture of at least one of ethylene glycol, butylene glycol and polytetramethylene glycol,

The dicarbonic acid may be one selected from the group consisting of dimethyl terephthalate (DMT) and dimethyl isophthalate (DMI), or a mixture of any of the above-described compositions with an anhydride resin

The polyol is characterized in that it can be composed of any one of poly (tetramethylene ether) glycol (PTMG), polyethylene glycol (PEG) and polypropylene glycol (PPG).

The dimethylisophthalate (DMI) is a dimethyl terephthalate (DMT) and a structural isomer.

The anhydride resin may also be selected from the group consisting of methyl tetrahydrophthalic anhydride (MeTHPA), methylhexahydrophthalic anhydride (MeHHPA), terahydrophthalic anhydride (THPA), and hexahydrophthalic anhydride And hydride (HHPA) may be added,

Although an anhydride resin in the above dicarbonic acid can be directly used as a starting material for the esterification reaction, it is also possible to use a conjugated diene having two double bonds and a maleic anhydride The product through a Diels-Alder reaction of maleic anhydride may also be used.

The esterification reaction of the polyetherester elastomer resin composition is described below. The esterification reaction is carried out with a low molecular weight diol component of butylene glycol and dimethyl terephthalate (DMT) to form a hard segment.

The molar fraction of dicarbonic acid and diol is 1: 1.0 ~ 1.5, and the excess diol component is mostly recovered through the depressurization process during condensation polymerization. (Dicarbonic acid) and Diol (Diol) have a value of 30 to 90% by weight in the whole elastic adhesive resin composition.

In addition, the dimethyl terephthalate (DMT) and the anhydride resin mixture may be composed of 80 to 95 mol% of dimethyl terephthalate (DMT) and 5 to 20 mol% of an anhydride resin .

In addition, the anhydride resin may have a molar ratio of methyl tertahydrophthalic anhydride (MeTHPA) and methyl hexahydrophthalic anhydride (MeHHPA) of 4 to 6 to 6 to 4.

Conventionally, aromatic or aliphatic tricarboxylic acids such as isophthalic acid, adipic acid and succinic acid have been used as a copolymerization raw material in order to control the melting point of a polyester-based elastic adhesive resin without using only dimethyl terephthalate (DMT)

The present invention relates to an anhydride resin such as methyltetrahydrophthalic anhydride (MeTHPA), methylhexahydrophthalic anhydride (MeHHPA), terahydophthalic anhydride (THPA), and hexahydrophthalic anhydride (HHPA) is added to terephthalate (DMT), it is possible to easily control various melting points required in the molding process of the final product while maintaining elastic properties and physical properties, which are important characteristics of the present invention .

Even when only a small amount of methyltetrahydrophthalic anhydride (MeTHPA) is substantially introduced, a melting point lowering phenomenon occurs, and a drop of about 4 ° C per mole can be obtained, and methyltetrahydrophthalic anhydride (MeTHPA), methyl When hexahydrophthalic anhydride (MeHHPA) is used in a molar ratio of 4 to 6 to 6 to 4, a lowering of the melting point occurs more greatly.

 For example, when mixed with MeTHPA alone, a decrease of about 5 ° C per 1 mole of the mixture results in a greater effect of lowering the melting point.

The catalyst used in the esterification reaction is selected from the group consisting of zinc acetate, sodium acetate, magnesium acetate, tetranomalbutoxy titanate, tetraisopropyl titanate, titanium oxide / silicon oxide microcopolymer, and nano titanate And is used in a range of 50 to 1000 ppm based on 100 parts by weight of the polyester based elastic adhesive resin. If the amount of the catalyst is insufficient, the esterification reaction rate is slowed. If the amount of the catalyst is insufficient, the thermal stability of the polyester- It gets worse.

After the esterification reaction, the condensation polymerization proceeds.

The oligomer solution obtained by the esterification reaction and the soft segment polyol were introduced into a pressure resistance and heat resistance reactor capable of undergoing vacuum decompression together with a condensation polymerization catalyst, a heat stabilizer and a photo stabilizer, and then a pressure of 760 to 1000 Torr and a pressure of 200 After an excessive amount of diol (Doil) is distilled off at a temperature of ~ 270 ° C, condensation polymerization is completed under a high vacuum of 1 mmHg or less to obtain a polyester elastomeric bonding resin of the present invention.

Here, the polyol may be selected from poly (tetramethylene ether) glycol (PTMG), polyethylene glycol (PEG) or polypropylene glycol (PPG), the molecular weight of the polyol is 400 to 20,000, 10 to 80% by weight based on the total weight of the resin.

The polymerization catalyst used in the condensation polymerization step may be one selected from the group consisting of antimony trioxide, antimony acetate, tetranormalbutoxy titanate, tetraisopropyl titanate, titanium oxide / silica oxide microcopolymer, and nano titanate And may be used in the range of 50 to 2000 ppm based on 100 parts by weight of the polyester-based elastic bonding resin.

The polyetherester elastomer resin prepared as described above is greatly improved in the melting point and the hot melt adhesive film layer produced using the same has a melting point (MP) of 80 to 160 ° C and an intrinsic viscosity (IV) of 1.0 to 1.8 .

Therefore, since it has a melting point lower than that of the conventional adhesive film, it is advantageous that the substrate layer and the polyurethane coating layer can be bonded without sewing lines by applying a relatively low temperature without heating to a high temperature.

The heat-bonded polyurethane coating composite has a flexural resistance of 30,000 or more at a temperature of -30 ° C. In general, the material may be cracked or broken when it is bent artificially in the subzero cold. The present invention is excellent in bending property even under cold and cold conditions, which is broken at over 30,000 bends.

In particular, the polyurethane coating composite according to the present invention, which has the feature of non-sewing, is widely used for running shoes with synthetic leather, so that it is excellent in utilization because it has many bending or twisting motions when it is used. In addition, it can be applied to various products in which synthetic leather can be used, such as clothes, goods, furniture, bags and so on.

The base layer is generally subjected to a water repellent treatment process, and the adhesive strength to the hot melt adhesive film layer after the above process is 4.0 kgf / in. And has the above characteristics.

The polyurethane coating layer is preferably used after being subjected to a dry coating treatment.

The features and other advantages of the present invention as described above will become more apparent from the following examples, which should not be construed as limiting or limiting the scope of protection of the present invention, .

Example  1,2

I) Production of hot melt adhesive film layer

The polyetherester elastomer resin (TPEE) was crystallized in a hot-air drying hopper with an agitator for 3 hours at a temperature of 80 ° C. and then dehydrated in a dehumidifying drying hopper at 80 ° C. for 8 hours Drying was carried out.

The basic physical properties of the raw material after drying are IV to 1.0 and below 1.8, Melting Point is 80 ° C or higher and 160 ° C or lower, and the water content is about 200 ppm. The melt index (MI) of the dried raw material is at an MI of 40 g / 10 min at 230 ° C.

A 50 μm thick, 100 μm low melting point elastic polyester (TPEE) film was prepared using a T-die facility after melting the resin using an extruder facility.

Ii) Production of polyurethane coating complex

A dry process was used to produce a polyurethane coating composite which is an artificial leather. The dry coated polyurethane was coated on the releasing paper, and the resultant was cured by heating at an appropriate temperature. After removing the releasing paper leaving only the cured urethane coating, Layer, and the polyurethane coating layer was obtained thereon. The polyurethane coating layer was pressed thereon under a pressure of 40 kg at a temperature of about 150 < 0 > C for 30 seconds to prepare a polyurethane coating composite which is an artificial synthetic leather.

Iii) Water repellent treatment of the base fabric layer

A 2.5% by weight aqueous solution of the composition consisting of 30% by weight of a hydroxylated perfluoroalkylethyl acrylate copolymer, 15% by weight of dipropylene glycol and 55% by weight of water was prepared, 0.3 parts by weight of silicone oil and 5 parts by weight of isopropyl alcohol were added to 100 parts by weight of the aqueous solution and sufficiently stirred to prepare a water repellent composition. Then, the polyester mesh fabric refined with a surfactant was immersed in the water repellent composition Dipping) to impregnate the water repellent composition.

Iv) In Example 1, the thickness of the hot-melt film layer was 50 탆, and in Example 2, it was 100 탆.

Comparative Example  1,2

In the comparative example, the hot melt film layer of the example was replaced with TPU product of Sambu Fine Chemical NASA, instead of the polyether ester elastomer resin (TPEE). The thickness of the film layer was 50 탆 for Comparative Example 1 and 100 탆 for Comparative Example 2 And the remaining conditions are the same as in the embodiment.

◎ Flexibility: ISO 5402: 2002

◎ Falling impact strength: ASTM D 1709

◎ Adhesive force measurement:

I) The low melting point elastic polyester (TPEE) film produced by the present invention and the thermoplastic polyurethane film (TPU) used in the comparative example are placed between the water repellent mash fabric.

Ii) Heat-press at a pressure of 5 kgf / cm2 and a temperature of 150 ℃ for 30 seconds on a hot press.

Iii) The heat-sealed samples were cut to a width of 1 inch and the tensile strength was measured according to ASTM D882 (Tensile Testing of Thin Plastic Sheet).

division Example Comparative Example One 2 One 2
Configuration

Polyurethane dry coating layer Polyurethane dry coating layer Hot melt film layer Sheet TPEE film TPEE film TPU film TPU film Thickness (㎛) 50 100 50 100 The substrate layer Water-repellent polyester mesh
Properties
Flexibility 30000 30000 10000 20000 Drop impact strength (g) 600 900 400 700 Adhesion (kgf / in.) 4.8 6.5 3.5 4.8

As shown in Table 1, the polyurethane coating composite composed of the hot melt film layer made of the low melting point elastic polyester (TPEE) film had a cold resistance of 30,000 times or more, a drop impact strength of 600 g or more, and an adhesive strength of 4.8 kgf / in. Respectively.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. It will be clear to those who have knowledge of

100: polyurethane coating composite 110: substrate layer
120: adhesive film layer 130: polyurethane coating layer

Claims (6)

A polyurethane coating composite comprising a substrate layer and a hot melt adhesive film layer composed of a polyether ester elastomer resin (PTEE) formed on the upper surface of the substrate layer and a polyurethane coating layer formed on the upper surface of the adhesive film layer,
The hot-melt adhesive film preferably has an intrinsic viscosity (IV) of 1.0 to 1.8, a melting point (MP) of 80 to 160 ° C, a flex resistance of 30,000 or more, and an adhesive strength of 4.0 kgf / in or more to a water- By weight, and is excellent in bending resistance and adhesive force.
The method according to claim 1,
The polyetherester elastomer resin is obtained by esterifying a diol and a dicarbonic acid as a raw material of a hard segment and polycondensation of a polyol as a soft segment raw material,
The diol may be composed of a mixture of at least one of ethylene glycol, butylene glycol and polytetramethylene glycol,
The dicarbonic acid may be any one selected from the group consisting of dimethyl terephthalate (DMT) and dimethyl isophthalate (DMI), or a mixture of any of the above-described compositions with an anhydride resin
Wherein the polyol is composed of any one of poly (tetramethylene ether) glycol (PTMG), polyethylene glycol (PEG) and polypropylene glycol (PPG).
3. The method of claim 2,
The anhydride resin may be selected from the group consisting of methyl tetrahydrophthalic anhydride (MeTHPA), methylhexahydrophthalic anhydride (MeHHPA), terahydrophthalic anhydride (THPA) and hexahydrophthalic anhydride (HHPA), wherein the hot-melt adhesive film is excellent in cold and cold bending properties and adhesive strength.
3. The method of claim 2,
The anhydride resin contains a product of a conjugated diene having two double bonds and a product of a Diels-Alder reaction of maleic anhydride. Wherein the hot-melt adhesive film is excellent in flex resistance and adhesion.
3. The method of claim 2,
The molecular weight of the polyol is 400 to 20,000,
Is 10 to 80% by weight relative to the polyetherester-based resin, characterized in that the hot-melt adhesive film is excellent in cold warpage resistance and adhesion.
A non-woven form shoe using a hot-melt adhesive film according to any one of claims 1 to 5.

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