WO2016182144A1 - Multilayer moisture-permeable waterproof film laminate comprising air-permeable thermoplastic hot-melt adhesive layer, and preparation method therefor - Google Patents

Abstract

The present invention relates to: a multilayer moisture-permeable waterproof film laminate comprising an air-permeable thermoplastic hot-melt adhesive layer, the laminate replacing a solvent-type adhesive, being flexible, having excellent moisture-permeability and waterproofness, maintaining excellent binding force between substrates and enabling a fragrance diffusion function to be provided for a long time when applied to a product to be worn on the human body; and a preparation method therefor. According to the present invention, provided is a multilayer moisture-permeable waterproof film laminate comprising an air-permeable thermoplastic hot-melt adhesive layer, the laminate comprising: a moisture-permeable substrate layer; an air-permeable thermoplastic hot-melt adhesive layer layered on one surface of the moisture-permeable substrate layer; and a moisture-permeable film layer made of a polyurethane resin and layered on one surface of the thermoplastic hot-melt adhesive layer.

Description

Multi-layer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer and a method of manufacturing the same

The present invention relates to a multi-layer moisture-permeable film laminate having a breathable thermoplastic hot melt adhesive layer and a method of manufacturing the same, and more particularly, to maintain the excellent inter-substrate binding while being flexible and excellent moisture-permeable waterproof, in place of the solvent-based adhesive, The present invention relates to a multi-layer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer that can also provide a fragrance dissipation function for a long time when applied to a product employed in the human body, and a manufacturing method thereof.

Footwear, such as hiking boots and sports shoes, and sportswear, such as mountaineering clothes, generally require excellent moisture permeability and waterproofness in addition to activity and lightness at the time of wearing.

"Water-permeable" refers to a property that does not pass water droplets, but that sweat or water vapor evaporates. The principle of obtaining "moisture permeability" and "waterproof" is that the size of water vapor and the size of water droplets (the diameter of water droplets is 1 mm or more and the diameter of water vapor is 0.0004 μm or less) are largely different from each other. When water is formed on the surface of the fabric, water vapor or carbon dioxide molecules from the skin are diverted to the outside through the space between the fibers and water droplets do not penetrate inside.

Technical methods for manufacturing the moisture-permeable waterproof fabric include a method of processing a high-density fabric using ultra-fine fibers, laminating a fine porous membrane on the fabric, or directly coating a moisture-permeable waterproof resin. Among the most active research results in the production of moisture-permeable waterproof foam is a laminating method of manufacturing a moisture-repellent waterproof fabric by coating a resin on a release paper to produce a hydrophilic non-porous or porous film and then bonding it with an adhesive fabric. In this case, there are two methods of bonding, dot bonding and front bonding, but dot bonding is mainly used for products requiring high functionality (high moisture permeability, soft touch).

Since the laminated body in which several base materials were laminated | stacked by such a dot-like bonding system usually has very few contacts with a base material and an adhesive agent, sufficient adhesive strength could not be maintained and peeling between base materials may arise. . In particular, when the garment etc. manufactured by the said method were washed with water, the adhesive strength of an adhesive agent fell remarkably under the influence of water, a detergent, etc., As a result, there existed a problem of peeling between base materials.

Accordingly, the present invention has been proposed to solve the above-mentioned problems, and it is flexible and has excellent moisture permeability waterproofing in place of the solvent-type adhesive, and maintains excellent binding force between substrates, when applied to a product employed in the human body SUMMARY OF THE INVENTION An object of the present invention is to provide a multilayer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer that can also provide an anti-balancing function for a time, and a method of manufacturing the same.

The problems of the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

According to an aspect of the present invention for achieving the above objects and other features, a moisture-permeable substrate layer; A breathable thermoplastic hot melt adhesive layer laminated on one surface of the moisture permeable base layer; And a moisture-permeable film layer made of a polyurethane resin laminated on one surface of the thermoplastic hot-melt adhesive layer. There is provided a multilayer moisture-permeable waterproof film laminate having a breathable thermoplastic hot-melt adhesive layer.

In one aspect of the invention, the moisture-permeable base layer is made of a fabric, the hot melt adhesive layer is characterized in that the melting point of 70 to 150 ℃.

In one aspect of the invention, (a) hydrophilic polyether polyols (45-55% by weight of one or more mixtures selected from the group consisting of Polyethylene Glycol, Polytetramethylene Glycol, Polypropylene Glycol), (b) glycol 5 to 15% by weight (1,4BD, 1,6HD, 1,5PD, HQEE, CHDM, MEG, DEG, MPD, or a mixture of two or more), (c) 4,4 ' 50 to 30% by weight of diphenylmethane diisocyanate was reacted in an amount such that the index, which is the molecular weight ratio of (c) to (a) + (b), in the range of 0.90 to 1.01, to have breathable physical properties. A thermoplastic polyurethane resin having a solid content of 100%, molded at a low melting point of ˜140 ° C., and 5-10% of a polyethylene glycol (PEG) having a molecular weight of 2,000 to 6,000 and a hydrophilic fumed silica of 0.5 to 2% in the thermoplastic polyurethane resin. It is a film formed by extrusion by addition, mixing and pelletizing resin. The breathable film layer preferably contains an antistatic agent.

In one aspect of the present invention, the multilayer moisture-permeable waterproof film laminate further includes a sprinkler shedding microparticles, wherein the scattering particles are i) 2.5 to 3.0 parts by weight of sodium stearate; 40 to 60 parts by weight of d-limonene; 25-50 parts by weight of 3-MMB and 10 to 22 parts by weight of fragrance oil, 95 to 50 parts by weight of oil gel fragrance or aqueous gel fragrance, and (ii) fragrance capsule encapsulated with thermosetting polymer resin or thermoplastic polymer resin. And 50 parts by weight.

In one aspect of the invention, the thermoplastic hot melt adhesive layer is characterized in that the thickness of 10 ~ 150um, the moisture-permeable film layer is characterized in that the thickness of 10 ~ 30um.

According to the multi-layer moisture-permeable waterproof film laminate having a breathable thermoplastic hot-melt adhesive layer of the present invention and a method for manufacturing the same, the product is adopted to the human body while maintaining excellent cohesion between substrates while being flexible and having excellent moisture-permeable waterproofing in place of a solvent-based adhesive. When applied to has an effect that can also provide a fragrance for a long time.

The effects of the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a cross-sectional view schematically showing the structure of a multilayer moisture-permeable waterproof film laminate comprising an adhesive layer with a breathable thermoplastic hot melt according to the present invention.

Figure 2 is an example of a process for producing a multi-layer moisture-permeable waterproof film laminate comprising an adhesive layer with a breathable thermoplastic hot melt according to the present invention, a schematic diagram showing the process of the top-down T-die extrusion and laminating composite line.

Further objects, features and advantages of the present invention can be more clearly understood from the following detailed description and the accompanying drawings. In addition, in the description with reference to the accompanying drawings, the same components regardless of reference numerals will be given the same reference numerals and duplicate description thereof will be omitted. In the following description of the present invention, if it is determined that the detailed description of the related known technology may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

Hereinafter, a multilayer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer according to the present invention and a manufacturing method thereof will be described.

First, a multilayer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer according to the present invention will be described with reference to FIGS. 1 and 2. 1 is a cross-sectional view schematically showing a structure of a multilayer moisture-permeable waterproof film laminate comprising an adhesive layer with a breathable thermoplastic hot melt according to the present invention, Figure 2 is a multilayer moisture-permeable film comprising an adhesive layer with a breathable thermoplastic hot melt according to the present invention As an example of a process for producing a laminate, it is a schematic diagram showing the process of the top-down T- dice extrusion and laminating composite line.

Multilayer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer according to the present invention, as shown in Figure 1, the moisture-permeable base layer (1); A breathable thermoplastic hot melt adhesive layer (2) laminated on one surface of the moisture permeable base layer (1); And it provides a multilayer moisture-permeable waterproof film laminate comprising a moisture-permeable film layer (3) made of a polyurethane resin bonded to the upper surface of the breathable thermoplastic hot melt adhesive layer (2).

The moisture-permeable base layer 1 is not limited to any kind of fibrous fabrics such as nonwoven fabrics, woven fabrics, and knitted fabrics. More specifically, the fabrics are made of nonwoven fabrics, cotton fabrics, ramie fabrics, synthetic fibers, and mixed fabrics thereof. It may be one or more selected from.

In addition, in the case where the moisture-permeable base layer 1 has a hole that is visible in appearance, the use of a solvent-based adhesive for the moisture-permeable base layer 1 reduces the contact point, in particular, lowers the adhesive strength of the moisture-permeable film layer, but the film form of the present invention. Since the breathable thermoplastic hot melt adhesive layer (2) of the contact is greatly increased, it is possible to implement a high adhesive force.

The breathable thermoplastic hot melt adhesive layer (2) is selected from the group containing (a) polyethylene glycol (Polyethylene Glycol), polytetramethylene glycol, polypropylene glycol (Polypropylene Glycol) so that the melting point is 70 to 150 ℃ 45-55 weight% of hydrophilic polyether polyols which consist of 1 type, or 2 or more types of mixtures, (b) 1,4 butanediol (1, 4- butane diol), 1, 6 hexanediol (1, 6 hexane diol), 1 1,5 Pentane Diol, Hydroquinonedi- (ß-hydrozyethyl) ether, Cyclohexandimethanol, Ethylene Glycol, Diethylene 5 to 15% by weight of glycols of one or two or more mixtures selected from the group consisting of glycol (Diethylene Glycol), 3-methyl 1,5-pentanediol (3-Methly 1,5-Pentandiol), (c 4,4'diphenyl methane diisocyanate 50 ~ 30 100% solids, which was formed at a low melting point of 130 to 140 ° C by having aerobic properties by reacting the amount% in an amount such that the index of the molecular weight ratio of (c) to (a) + (b) becomes 0.90 to 1.01. Phosphorus thermoplastic polyurethane resin.

In addition, (a) has an average molecular weight of about 2000, and forms a soft segment by reacting with isocyanate in the polyurethane chemical structure, and uses 45 ~ 55 wt% of hydrophilic polyol, which is superior to general thermoplastic polyurethane. It can be made to have the physical properties, extrusion processability suitable for hot melt.

(B) Glycols 1,4BD (1,4-Butane Diol), 1,6HD (1,6hexane Diol), 1,5PD (1,5Pentane Diol), HQEE (Hydroquinonedi- (ß-hydrozyethyl) ether) , CHDM (Cyclohexandimethanol), MEG (Ethylene Glycol), DEG (Diethylene Glycol), MPD (3-Methly 1,5-Pentandiol) selected from the group containing one or two or more kinds of average molecular weight of about 50 ~ 150 In this case, it acts as a chain extender of the polyurethane reaction to form a hard segment portion, and determines the elasticity and flexibility in the composition of 5 to 15% by weight, and exhibits a low melting point polyurethane hot melt property of hardness 70 ~ 75A.

In addition, the diisocyanate (c) in the composition is used for the production of polyurethane, in particular containing toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate in aromatic diisocyanate It may be one kind or a mixture of two or more kinds selected from the group.

Here, in order to further increase the moisture permeability of the thermoplastic hot melt adhesive layer 2, 5 to 10% of polyethylene glycol (PEG) having a molecular weight of 2,000 to 6,000 and 0.5 to 2% of hydrophilic fumed silica are added and mixed in a mixer such as a Henschel mixer. The resin is then pelletized in a twin screw type compounding machine.

In addition, the resin pelletized in the compounding machine is composed of two unwinding rollers and a single screw T-die extrusion and laminating composite line of two types simultaneously fed from both sides based on a film on which a substrate to be deposited is melted and extruded. At one side of the unwinding roller is mounted on the moisture-permeable substrate layer (1) and on the other side through the moisture-permeable film layer (3) made of polyurethane resin, while simultaneously introducing the deposition layer on both sides of the breathable between the layers The thermoplastic hot melt adhesive layer 2 is extruded to a thickness of 10 to 150 um, and then pressed while passing between the elastic roll into which the cooling water flows and the steel roll, and is wound in a roll of an appropriate length in a winding roller via a take-up line (FIG. 2). Reference).

More specifically, when the raw material for the breathable thermoplastic hot melt adhesive layer 2 is put into the extruder hopper in a dehumidified and dried state, the raw material is divided into three to six zones cylinders designed to control the temperature for each zone; An adapter connected to the cylinder and connected to the T-dice 6; And a hot-melt adhesive layer 2 in a molten film state, which is connected to the adapter, is divided into 5 to 7 zones, and is designed to control the temperature and the gap of the opening portion for each zone. Extruded. The breathable thermoplastic hot melt adhesive layer (2) comprises a moisture vapor barrier layer (1) supplied from the first unwinding roller (4); And the moisture permeable film layer 3 made of a polyurethane resin supplied from the second unwinding roller 5 to be pressed and cooled by the elastic touch roll 7 and the cooling & pattern roll 8.

Subsequently, the multi-layer moisture-permeable waterproof film laminate comprising the breathable thermoplastic hot melt laminated layer in the rolled state in the rewinder 10 through the cooling roll 9 to form the multi-layer moisture-permeable waterproof film laminate composed of the adhesive layer with the breathable thermoplastic hot melt. It can be prepared.

Next, the moisture-permeable film layer 3 made of a polyurethane resin is generally used in the art, and the type thereof is not particularly limited. However, the moisture-permeable film layer 3 having a thickness of 10 to 30 μm and high moisture permeability can be preferably used. Here, the moisture-permeable film layer 3 which consists of polyurethane resins can use the thing which added antistatic agent and added antistatic property.

On the other hand, the multilayer moisture-permeable waterproof film laminate of the present invention further includes a fragrant volatile particles. The micro-acid particles are included in or included in at least one of the moisture-permeable base layer 1, the thermoplastic hot melt adhesive layer 2, and the water-permeable film layer 3, i) 2.5 to 3.0 parts by weight of sodium stearate; 40 to 60 parts by weight of d-limonene; 25-50 parts by weight of 3-MMB and 10 to 22 parts by weight of fragrance oil, 95 to 50 parts by weight of oil gel fragrance or aqueous gel fragrance, and (ii) fragrance capsule encapsulated with thermosetting polymer resin or thermoplastic polymer resin. 50 parts by weight.

The flavor capsule is a natural polymer or polyurethane-based; Melamine type; 30 to 40 parts by weight of fragrance oil is added to a mixture of 1 to 3 parts by weight of the polymer resin selected from the epoxy system, 0.5 to 2 parts by weight of sodium hydroxide and 40 to 50 parts by weight of water, and then emulsified. It is preferable to add -0.5 weight part, 2 to 3 weight part of melamine, and 2 to 4 weight part of triethylamine, and to stir, heating at 40-80 degreeC.

As described above, it is possible to manufacture a multilayer moisture-permeable waterproof film laminate comprising an adhesive layer made of breathable thermoplastic hot melt having various thicknesses and appearances.

On the other hand, the moisture-permeable base layer (1); A breathable thermoplastic hot melt adhesive layer (2) bonded to one surface of the moisture-permeable base layer (1); And a moisture-permeable film layer 3 made of a polyurethane resin bonded to the upper surface of the breathable thermoplastic hot melt adhesive layer is as follows.

First, as described above, there is a method of melting and extruding the breathable thermoplastic hot melt adhesive layer 2 therebetween while simultaneously inserting the adherend layer on both sides, thereby completing the production in one step. In this case, the process can be drastically reduced, and since the release paper does not need to be used to produce a hot melt film separately, the cost can be greatly reduced.

Second, in addition to the above method, if there is a problem in the equipment, etc., first the extrusion of the breathable thermoplastic hot melt adhesive layer (2) on one surface of the moisture-permeable base layer (1) supplied from one unwinding roller, and again equipped with heating facilities A two-step method of laminating the moisture-permeable film layer 3 made of a polyurethane resin in a true dry lamination machine can be used.

Third, the breathable thermoplastic hot melt adhesive layer 2 is first extruded onto a release paper (including PP, PE, PET, and silicone release-treated paper) supplied from one unwinding roller, and the moisture-permeable base layer 1 It is possible to use three-stage method of laminating the moisture-permeable film layer (3) made of polyurethane resin in a dry lamination machine equipped with heating facilities again on one side of the sheet, and again removing the release paper. It is most preferable to use this because it can reduce the process loss, additional process cost, and the additional cost of using the release paper.

Hereinafter, examples and test examples according to the experimental results of the present invention will be described. The following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

Example

According to the process diagram shown in Figure 2, a multilayer moisture-permeable waterproof film laminate comprising an adhesive layer made of a breathable thermoplastic hot melt was prepared. More specifically, the moisture permeable base layer 1 supplied from the first unwinding roller 4 in a single screw T-die extruder having a cylinder diameter of 120 mm and an L / D ratio of 30: 1; And a breathable thermoplastic hot melt adhesive layer 2 extruded through the T-dice 6 between the moisture-permeable film layers 3 made of the polyurethane resin supplied from the second unwinding roller 5. ) And cold / pattern rolls 8 for compression and cooling.

At this time, the cylinder 1 of the extruder 130 ℃ 2 140 ℃ 3 150 ℃ 4 160 ℃ 5 times 165 ℃ and head portion 160 ℃ T-Dice was set to 160 ℃ the same from 1 to 7 times.

The screw RPM of the extruder was 10rpm / min and the line speed was 12m / min. The adhesive layer was extruded with a breathable thermoplastic hot melt with a thickness of 100um, and again the line speed was changed to 24m / min with a breathable thermoplastic hotmelt with a thickness of 50um. Was extruded.

Subsequently, the multilayer moisture-permeable waterproof film laminate having the adhesive layer made of the breathable thermoplastic hot melt is wound in a roll state by the rewinder 10 via a cooling roll 9 to produce the multilayer moisture-permeable waterproof film laminate product having the adhesive layer made of breathable thermoplastic hot melt. Prepared. At this time, the high-density plain weave woven from Nylon 20 denia was used as the moisture vapor transmission base layer (1).

And as the moisture-permeable film layer 3 which consists of polyurethane resins, the moisture-permeable waterproof film of 15um thickness of TECONE Co., Ltd. of Japan was used. The raw material of the breathable thermoplastic hot melt adhesive layer (2) used EP-775A, a moisture-permeable hot melt resin of Dong-A Chemical, and an additive to further increase the moisture permeability. After adding 1% of OCI's hydrophilic fumed silica K300 to improve moisture permeability and flowability, the mixture was heated and mixed for 20 minutes while heating at 40 ° C. in a Henschel mixer, and the mixed resin was put back into a twin screw type compounding machine. To prepare a resin of pellet type.

Test Example

For the multilayer moisture-permeable film laminate comprising the adhesive layer made of the breathable thermoplastic hot melt prepared in the above example, the moisture permeability was measured according to ASTM E96-2000, INVERTED CUP WATER METHOD, and the water pressure was measured according to JISL1092B. It is shown in Table 1 below.

Table 1

division	Breathable Hot Melt Layer Thickness (um)	Water pressure resistance (mm / H2O)	Breathability (g / m2 * 24h)
			Primary	Secondary	Average
One	50	More than 10,000	19,342	24,459	21,901
2	100	More than 10,000	21,838	17,346	19,592

As shown in Table 1, it was confirmed that the multilayer moisture-permeable waterproof film laminate composed of the adhesive layer with the breathable thermoplastic hot melt according to the embodiment of the present invention has excellent water resistance and moisture permeability.

As described above, the multilayer moisture-permeable waterproof film laminate of the adhesive layer made of a breathable thermoplastic hot melt according to the present invention has various effects that are flexible while replacing the solvent-type adhesive faced with VOC regulation and have excellent adhesion and moisture-permeability. In addition, since it has excellent breathability even in a thick adhesive layer of about 150um, in addition to products requiring thin films, such as clothing, it can be very usefully applied even in fields requiring a breathable hot melt film of considerable thickness, such as footwear.

The embodiments and the accompanying drawings described herein are merely illustrative of some of the technical ideas included in the present invention. Therefore, since the embodiments disclosed herein are not intended to limit the technical spirit of the present invention, but to explain, it is obvious that the scope of the technical spirit of the present invention is not limited by these embodiments. Modifications and specific embodiments that can be easily inferred by those skilled in the art within the scope of the technical idea included in the specification and drawings of the present invention should be construed as being included in the scope of the present invention.

1: breathable substrate layer

2: breathable thermoplastic hot melt adhesive layer

3: moisture vapor film layer

4: first unwinding roller

5: second unwinding roller

6: T-dice

7: elastic touch roll

8: cooling / pattern roll

9: cooling roll

10: winding roller

Claims (4)

1. Moisture-permeable base material layer 1;

   A breathable thermoplastic hot melt adhesive layer (2) laminated on one surface of the moisture permeable base layer (1); And

   And a moisture-permeable film layer (3) made of a polyurethane resin laminated on one surface of the thermoplastic hot melt adhesive layer (2).

   The thermoplastic hot melt adhesive layer (2)

   (a) Hydrophilic polyether polyols consisting of one or two or more mixtures selected from the group consisting of polyethylene glycol, polytetramethylene glycol, and polypropylene glycol % By weight, (b) 1,4-butanediol (1,4-Butane Diol), 1,6 hexanediol (1,6hexane Diol), 1,5 pentanediol (1,5Pentane Diol), hydroquinonedi- (ß- Hydroquinyl) ether (Cyclohexandimethanol), ethylene glycol (Ethylene Glycol), diethylene glycol (Diethylene Glycol), 3-methyl 1,5-pentanediol (3- 5 to 15% by weight of glycols of one or more mixtures selected from the group consisting of Methly 1,5-Pentandiol), (c) 4 to 4'diphenylmethane diisocyanate 50 to 30 The exponent, which is the molecular weight ratio of (c) to (a) + (b), is 0.90 to 1.01 It was reacted by the term tube having the physical properties a, solid content 100%, the thermoplastic polyurethane resin forming the low melting point of 130 ~ 140 ℃; And a resin obtained by adding, mixing and pelletizing 5-10% of polyethylene glycol having a molecular weight of 2,000-6,000 and 0.5-2% of hydrophilic fumed silica to the thermoplastic polyurethane resin. Features,

   The moisture-permeable film layer 3 contains an antistatic agent

   Multi-layer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer.
2. The method according to claim 1,

   The moisture permeable base layer 1 is made of a fabric,

   The hot melt adhesive layer 2 is characterized in that the melting point is 70 to 150 ℃

   Multi-layer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer.
3. The method according to claim 1,

   The multi-layer moisture-permeable film laminate further includes a fragrant shedding particles,

   The aromatic acid fine particles are i) 2.5 to 3.0 parts by weight of sodium stearate; 40 to 60 parts by weight of d-limonene; 25-50 parts by weight of 3-MMB and 10 to 22 parts by weight of fragrance oil, 95 to 50 parts by weight of oil gel fragrance or aqueous gel fragrance, and (ii) fragrance capsule encapsulated with thermosetting polymer resin or thermoplastic polymer resin. 50 parts by weight

   Multi-layer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer.
4. The method according to claim 1,

   The thermoplastic hot melt adhesive layer 2 has a thickness of 10 ~ 150um,

   The moisture-permeable film layer 3 is characterized in that the thickness of 10 ~ 30um

   Multi-layer moisture-permeable waterproof film laminate having a breathable thermoplastic hot melt adhesive layer.

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