JP2007191810A - Highly foamed fabric having polyurethane microporous membrane, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide highly foamed fabrics having moisture permeating and water resisting properties by utilizing a foaming method by which method thermally expandable microcapsules are not broken and expansion thereof is not inhibited. <P>SOLUTION: The highly foamed fabric is obtained by sequentially laminating and sticking a polyurethane microporous membrane, a barrier layer, a highly foamed layer and a fabric. The microporous membrane is obtained by wet coagulation of polyurethane-based resin solution using N,N-dimethylformamide as a main solvent. The barrier layer is a polyurethane-based thin film layer inhibiting permeation of N,N-dimethylformamide. The highly foamed layer comprises thermally expanded microcapsules, a polyurethane-based resin holding the microcapsules on one surface of the fabric and hydrophilic microporous silica fine powder existing on the surface of the microcapsules or in the polyurethane-based resin. Thereby, as the barrier layer exists and the surfaces of the microcapsules are hardly dissolved in the N,N-dimethylformamide so high foaming is realized and the moisture permeating, water resisting and highly foamed fabric can be obtained. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a highly foamed fabric provided with a polyurethane microporous membrane and a method for producing the same, and in particular, a high moisture permeability and waterproof property suitable for use as various clothing fabrics such as casual clothing, sports clothing, and mountaineering clothing. The present invention relates to a foam fabric and a method for producing the same.

  Conventionally, as a fabric excellent in moisture permeability and waterproofness, a fabric in which a polyurethane microporous film is laminated and bonded is known. In this moisture-permeable and waterproof fabric, a polyurethane resin solution containing N, N-dimethylformamide as a main solvent is applied to one side of the fabric, and then the applied polyurethane resin solution is immersed in water or the like, It is obtained by solidifying to form a polyurethane microporous membrane.

  As the fabric to which the polyurethane resin solution is applied, generally a knitted fabric or a nonwoven fabric is used. The synthetic fibers include polyamide-based synthetic fibers represented by nylon 6 and nylon 66, polyester-based synthetic fibers represented by polyethylene terephthalate, polyacrylonitrile-based synthetic fibers, polyvinyl alcohol-based synthetic fibers, and semi-synthetic fibers such as triacetate. Natural fibers such as fibers and cotton are used alone or in combination. Therefore, even when a polyurethane-based resin solution containing N, N-dimethylformamide as a main solvent was applied, there was little risk of the fabric being attacked.

  However, in recent years, in order to impart a three-dimensional effect to a fabric, a resin layer containing thermally expandable microcapsules is laminated and bonded to the fabric, and then the microcapsules are thermally expanded. For example, in Patent Document 1, a printing ink containing a thermally expandable microcapsule is printed in a pattern (pattern shape) on the surface of a base material, and then the thermally expandable microcapsule is expanded by heating to make it uneven. It is described that a pattern printed leather with excellent three-dimensional effect is obtained. Moreover, in patent document 2, after printing the polyurethane resin solution containing a thermally expansible microcapsule on the base material surface in a pattern form (pattern shape) by the silk screen printing method, a colored layer is provided on the surface, and then It is described that a thermally expandable microcapsule is expanded by heating to obtain a laminate having excellent unevenness and rich three-dimensionality.

JP-A-60-246878 (Claims) JP 10-329297 A (paragraph numbers 0025 and 0026)

  The inventor has attempted to obtain a moisture-permeable and waterproof fabric using such a fabric rich in three-dimensional effect. That is, after laminating and laminating a resin layer containing thermally expandable microcapsules, a polyurethane resin solution containing N, N-dimethylformamide as a main solvent was applied to the surface of the resin layer, and subsequently applied. A polyurethane resin solution is immersed in water or the like and wet-solidified to form a polyurethane microporous film. And after that, by heating, the microcapsule was thermally expanded, and it was trying to obtain the moisture-permeable waterproof fabric rich in a three-dimensional effect.

  However, since the heat-expandable microcapsules are made of a thermoplastic resin such as vinylidene chloride-acrylonitrile copolymer as an outer shell, and a heat-expandable gas such as isobutane is encapsulated in the outer shell, When N, N-dimethylformamide, which is the main solvent of the resin solution, permeates, the outer shell sometimes dissolves. For example, when the thermally expandable microcapsules are not sufficiently embedded in the resin layer and are exposed on the surface of the resin layer, the outer shell may be dissolved. Therefore, in such a case, after applying the polyurethane resin solution, many of the microcapsules exposed on the surface of the resin layer have disappeared, and part of the microcapsules cannot be thermally expanded. In addition, a moisture-permeable and waterproof fabric rich in volume and three-dimensionality could not be obtained.

  Therefore, the present invention provides a barrier layer on the surface of the resin layer containing the thermally expandable microcapsules so that the thermally expandable microcapsules are not attacked by N, N-dimethylformamide, which is the main solvent of the polyurethane resin solution. It is a thing.

  That is, the present invention comprises a polyurethane microporous membrane, a barrier layer, a highly foamed layer, and a fabric laminated in this order, and the polyurethane microporous membrane is a polyurethane-based resin containing N, N-dimethylformamide as a main solvent. The solution is obtained by wet coagulation, the barrier layer is a polyurethane-based thin film layer that inhibits permeation of the N, N-dimethylformamide, and the highly foamed layer includes thermally expanded microcapsules and The microcapsule is formed of a polyurethane resin for holding the microcapsule on one side of the fabric, and a hydrophilic and microporous silica fine powder existing on the surface of the microcapsule or in the polyurethane resin. The present invention relates to a highly foamed fabric having a featured polyurethane microporous membrane and a method for producing the same.

  In the present invention, as the fabric, those generally used as clothing materials such as woven fabric, knitted fabric, non-woven fabric, and synthetic leather can be used. This is because the highly foamed fabric according to the present invention can be suitably used as various clothing materials such as casual clothing, sports clothing, and mountaineering clothing.

  As the fiber constituting the fabric, any conventionally known fiber can be used. For example, polyamide synthetic fiber represented by nylon 6 and nylon 66, polyester synthetic fiber represented by polyethylene terephthalate, polyacrylonitrile synthetic fiber, polyvinyl alcohol synthetic fiber, semi-synthetic fiber such as triacetate, cotton, etc. Natural fibers can be used alone or in combination.

  A water repellent treatment may be performed on one or both surfaces of the fabric to provide a water repellent layer. In particular, it is preferable to use a fabric having a water repellent treatment on the surface on which the high foam layer is laminated and bonded. This is because when the highly foamed layer is laminated and bonded, the highly foamed layer can be prevented from penetrating deeply into the fabric or oozing out to the back of the fabric. As the water repellent used for the water repellent treatment, known ones such as a paraffin water repellent, a polysiloxane water repellent, or a fluorine water repellent can be used. The water repellent treatment may be performed by a known method such as a padding method or a spray method. In particular, when good water repellency is required, padding with a 5% aqueous dispersion of a fluorine-based water repellent, for example, AG7000 (made by Asahi Glass Co., Ltd., fluorine-based water repellent emulsion) ), And a method of performing heat treatment at 150 to 170 ° C. for 30 seconds to 2 minutes may be employed.

  The highly foamed layer is basically formed of a polyurethane resin, thermally expanded microcapsules, and hydrophilic and microporous silica fine powder. The polyurethane resin is a copolymer obtained by reacting a polyisocyanate component and a polyol component. As the polyisocyanate component, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and the like are used alone or in combination. Specifically, tolylene-2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate or trifunctional or higher functional isocyanate is used alone or in combination. Moreover, polyether polyol, polyester polyol, etc. are used as a polyol component. As the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like is used alone or in combination. As the polyester polyol, for example, a reaction product of a diol such as ethylene glycol or propylene glycol and a dibasic acid such as adipic acid or sebacic acid, a ring-opening polymer such as caprolactone, or the like is used.

  In the polyurethane-based resin, it is preferable to add and mix an isocyanate-based compound in order to improve the adhesive strength with the fabric and improve the peel resistance of the highly foamed layer. Examples of the isocyanate compound include tolylene-2,4-diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or a compound containing 3 moles of these diisocyanates and active hydrogen (for example, trimethylolpropane, glycerin, etc. ) Triisocyanates obtained by addition reaction with 1 mol can be used. The isocyanate compound may be in a form in which the isocyanate group is liberated, or may be in a form in which an additional block is formed with phenol, lactam, methyl ketone, etc., and dissociated by heat treatment. What is necessary is just to use properly according to a use. As for the usage-amount of the isocyanate compound to add and mix, it is desirable to use in the ratio of 0.1-10 mass parts with respect to 100 mass parts of polyurethane-type resins in a highly foamed layer. If the amount used is less than 0.1 parts by mass, the adhesive strength to the fabric tends not to improve much. Moreover, when the usage-amount exceeds 10 mass parts, there exists a tendency for a texture to harden | cure.

  The thermally expanded microcapsule is obtained by expanding a thermally expandable microcapsule under heating. Any thermally expandable microcapsule can be used as long as it is conventionally known. Specifically, the particle diameter is about 5 to 50 μm, and the outer shell is formed of a thermoplastic resin made of a polymer such as vinylidene chloride or acrylonitrile, and isobutane, isopentane, n-pentane is formed in the outer shell. Thermally expandable microcapsules in which low boiling point hydrocarbons such as are encapsulated can be used. Such thermally expandable microcapsules expand about 20 to 70 times in volume under heating at about 80 to 200 ° C. Therefore, the microcapsules thermally expanded in a completely free state have a particle size of about 13 μm to 2.1 mm.

  As the hydrophilic and microporous silica fine powder, any conventionally known fine powder can be used. For example, it is manufactured by a wet method (gel method, sedimentation method) or dry method, and has a hydrophilic and microporous silica fine powder having OH groups that are hydrophilic groups on the surface and a large number of pores. be able to. The reason for using hydrophilic and microporous silica fine powder is that when this is used in combination with a thermally expandable microcapsule, the microcapsule foams well. For this reason, the principle of whether the thermally expandable microcapsule easily expands when it is hydrophilic, microporous, or silica fine powder is not clear. However, as a result of the demonstration conducted by the present inventors, it has been found that the thermally expandable microcapsules expand well only when hydrophilic and microporous silica fine powder is used. Therefore, in the present invention, hydrophilic and microporous silica fine powder is present in the highly foamed layer.

  The particle diameter of the silica fine powder is about 0.01 to 200 μm, and particularly about 1 to 100 μm. In the present invention, when the particle diameter of the silica fine powder is equal to or larger than the particle diameter of the thermally expandable microcapsule, the foamability is further improved. The reason for this is not clear, but it can be assumed that the gap between the silica fine powders is a gap that allows expansion of the thermally expandable microcapsules.

  The content ratio of each substance in the highly foamed layer is preferably the following ratio. That is, the thermally expanded microcapsule is preferably 3 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyurethane resin. When the thermally expanded microcapsule is less than 3 parts by mass, the three-dimensional effect of the highly foamed layer tends to be poor. When the amount of the microcapsule exceeds 50 parts by mass, the amount of the polyurethane-based resin is relatively reduced, so that it becomes difficult to hold the microcapsule with the polyurethane-based resin, and the microcapsule tends to drop off. The hydrophilic and microporous silica fine powder is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the synthetic resin. When the silica fine powder is less than 3 parts by mass, it tends to be difficult to improve the foamability of the thermally expandable microcapsules. Moreover, when a silica fine powder exceeds 50 mass parts, the tendency for a highly foamed layer to become hard will arise. Furthermore, the ratio of the thermally expanded microcapsules and silica fine powder is preferably microcapsules: silica fine powder = 1: 3 to 3: 1 (parts by mass). If the proportion of silica fine powder or microcapsules used is large beyond this range, the foamability of the thermally expandable microcapsules tends to be difficult to improve.

  The highly foamed layer may be laminated and bonded to the entire surface of one side of the fabric, or may be laminated and bonded as a pattern in a pattern. When used as a material for clothing, it is preferable from the viewpoint of fashionability and design to be laminated in a pattern. The pattern shape may be any pattern, but it is a dot pattern, grid pattern, linear pattern, diagonal pattern, pyramid pattern, turtle shell pattern, uniform pattern such as a specific trademark pattern, or a random pattern. It is preferable that the design has an attractive appearance that easily exhibits design properties such as the above. Further, the area occupied by the patterned pattern on one side of the fabric is preferably in the range of 5 to 90%, more preferably in the range of 10 to 80%. When the occupied area is less than 5%, there is a tendency that the three-dimensional effect is poor and it is difficult to obtain an excellent design. Further, when the occupied area exceeds 90%, the texture tends to become hard.

  A barrier layer is laminated and bonded to the surface of the highly foamed layer. The barrier layer is a polyurethane-based thin film layer and inhibits the permeation of N, N-dimethylformamide. That is, this is for preventing the N, N-dimethylformamide used from penetrating into the highly foamed layer when forming a polyurethane microporous film on the highly foamed layer. Any polyurethane-based resin for forming the polyurethane-based thin film layer can be used as long as it is conventionally known. Specifically, those listed above can be used. The barrier layer may be provided on the entire surface of the fabric, or when the high foam layer is laminated and bonded in a pattern, the barrier layer may be provided only at the location of the pattern high foam layer. That is, the barrier layer may be provided in synchronization with the pattern of the highly foamed layer. The thickness of the barrier layer is preferably 0.5 to 10 μm, more preferably 1 to 8 μm. If it is less than 0.5 μm, there is a tendency that it is difficult to inhibit the permeation of N, N-dimethylformamide. Moreover, when it exceeds 10 micrometers, the tendency for the texture of a highly foamed fabric to fall arises.

  A polyurethane microporous film is formed on the surface of the barrier layer. The polyurethane microporous membrane is obtained by wet coagulation of a polyurethane resin solution containing N, N-dimethylformamide as a main solvent. That is, a polyurethane resin solution containing N, N-dimethylformamide as a main solvent is applied to the surface of the barrier layer and then immersed in water or a water-based N, N-dimethylformamide mixture to solidify the polyurethane resin. It is obtained by a known wet coagulation method. For the microporous polyurethane membrane, from the viewpoint of improving the quality and functionality of the membrane, fillers such as titanium dioxide and calcium carbonate, organic or inorganic pigments, lubricants such as silicon dioxide, zeolite deodorants, photocatalysts A titanium oxide antibacterial agent having a function may be contained.

The thickness of the polyurethane microporous membrane is preferably 5 to 200 μm, more preferably 10 to 100 μm. When the thickness is less than 5 μm, the volume feeling and durability of the highly foamed fabric tend to be insufficient. Moreover, when thickness exceeds 200 micrometers, the tendency which becomes disadvantageous from the surface of processing cost arises. The microporosity of the polyurethane microporous membrane is preferably 20 to 80%, more preferably 40 to 70%. If the microporosity is less than 20%, the moisture permeability tends to be insufficient. If the microporosity exceeds 80%, the strength of the polyurethane microporous membrane tends to decrease. The microporosity is simply {[1-dry resin coating amount (coating amount per 1 m ² )] / [average film thickness (μm) × 1.2 (specific gravity of polyurethane resin)] × 100}. It is calculated from the equation.

  In the present invention, a surface layer may be further provided on the polyurethane microporous membrane. This surface layer can be provided when it is desired to further impart washing durability, waterproofness, etc. to the highly foamed fabric. Specifically, it is preferable to employ a polyurethane-based thin film layer similar to the barrier layer as the surface layer. When it is desired to impart water repellency to a highly foamed fabric, a conventionally known water repellency treatment may be applied to the polyurethane microporous membrane or surface layer.

  The highly foamed fabric according to the present invention can be suitably obtained by the following production method. That is, a synthetic resin solution containing a thermally expandable microcapsule, a hydrophilic and microporous silica fine powder, and a polyurethane-based resin is applied to one side of the fabric, and then dried to form a synthetic resin layer. A step of forming a barrier layer comprising a polyurethane-based thin film layer by laminating and laminating a polyurethane-based thin film layer that inhibits permeation of N, N-dimethylformamide on the surface of the synthetic resin layer, and the surface of the barrier layer A polyurethane resin solution containing N, N-dimethylformamide as a main solvent, followed by wet coagulation of the polyurethane resin solution to form a polyurethane microporous film; And a step of expanding the expandable microcapsule.

  First, a synthetic resin liquid in which a polyurethane resin is dissolved or dispersed in water and / or an organic solvent is prepared. Then, in this synthetic resin liquid, thermally expandable microcapsules and hydrophilic and microporous silica fine powder are added and mixed to obtain a synthetic resin solution. The type and amount of polyurethane resin, the type and addition amount of thermally expandable microcapsules, and the addition amount of hydrophilic and microporous silica fine powder are as described above. This synthetic resin solution is applied to one side of the fabric. This application may be applied to the entire surface of one side of the fabric or may be applied in a pattern. As a coating method, a comma coating method, a roll-on knife coating method, a gravure coating method, a screen printing method, or the like may be employed. After the application, the synthetic resin solution is dried to solidify the polyurethane resin to form a synthetic resin layer. The thickness of the synthetic resin layer is preferably about 5 to 200 μm, more preferably about 10 to 100 μm. The polyurethane resin may be crosslinked at this stage or may be in an uncrosslinked state.

  After forming the synthetic resin layer, a barrier layer is formed on the surface of the synthetic resin layer. There are various methods for forming the barrier layer depending on the type of the barrier layer. For example, when a polyurethane-based thin film is used, it may be bonded to the surface of the synthetic resin layer with an adhesive or the like. When a polyurethane resin solution is used, it may be applied by a floating knife coating method, reverse coating method or gravure coating method, and then dried to solidify the resin solution to form a polyurethane thin film layer. . Furthermore, when a barrier layer is formed in synchronization with the pattern of the synthetic resin layer formed in a pattern, a polyurethane-based thin film layer is formed by a polyurethane-based resin solution and a printing method using a rotary screen or a flat screen. A barrier layer may be provided.

  After forming the barrier layer, a polyurethane resin solution containing N, N-dimethylformamide as a main solvent is applied to the barrier layer surface. As a coating method, a comma coating method, a roll-on knife coating method, or the like may be employed. And after application | coating, it immerses in 5-40 degreeC water or the water-based N, N-dimethylformamide liquid mixture, and solidifies a polyurethane-type resin. Then, if it wash | cleans in hot water of 40-80 degreeC and it dries, a polyurethane microporous film will be obtained. The polyurethane microporous membrane provides a highly foamed fabric having excellent waterproofness and moisture permeability.

  After obtaining the laminated body laminated | stacked in order of the cloth, the synthetic resin layer, the barrier layer, and the polyurethane microporous film as described above, the mixture is heated to about 80 to 200 ° C. Inflate. Thereby, a synthetic resin layer turns into a highly foamed layer. The thickness of the high foam layer is about several times the thickness of the synthetic resin layer. That is, when the thickness of the synthetic resin layer is about 10 to 100 μm, the thickness of the highly foamed layer is about 30 to 500 μm. As described above, a surface layer made of a polyurethane-based thin film may be provided on the surface of the polyurethane microporous membrane in order to further impart waterproofness.

  As described above, the highly foamed fabric according to the present invention has excellent moisture permeability and waterproofness, and also has a highly foamed layer. is there. Therefore, it is suitable for use as a fabric for various clothing such as casual clothing, sports clothing, and mountaineering clothing.

  The present invention provides a barrier layer on the surface of a synthetic resin layer containing a thermally expandable microcapsule, a hydrophilic and microporous silica fine powder, and a polyurethane resin, and then N, N-dimethyl on the barrier layer surface. A polyurethane resin solution containing formamide as a main solvent is applied. Therefore, N, N-dimethylformamide is prevented from penetrating into the synthetic resin layer by the barrier layer, and as a result, the outer shell of the thermally expandable microcapsule can be prevented from dissolving. Therefore, when the polyurethane resin solution is wet-coagulated to form a polyurethane microporous film and then heated, the thermally expandable microcapsules are well expanded.

  As described above, the foamed layer obtained using the synthetic resin solution containing the thermally expandable microcapsule and the hydrophilic and microporous silica fine powder has the effect of being highly foamed and rich in volume and three-dimensional effect. It plays. In addition, in the present invention, high foaming is realized by using a thermally expandable microcapsule and a hydrophilic and microporous silica fine powder in combination. The action of both is not clear, but the inventor presumes as follows. That is, when only the heat-expandable microcapsules are mixed in the synthetic resin solution, it is presumed that after the synthetic resin solution is applied on one side of the fabric, it is likely to be unevenly distributed in a partially dense state. On the other hand, when hydrophilic and microporous silica fine powder coexists in the synthetic resin solution, the heat-expandable microcapsules are less likely to be unevenly distributed and are relatively uniformly dispersed in the polyurethane resin. I guess it exists in a rough state. As a result, the thermally expandable microcapsules exist in a relatively free state, and it is assumed that they may expand smoothly.

Example 1
[Preparation of fabric]
Nylon multifilaments of 78 dtex / 48 filaments were used for both the warp and the weft, and a taffeta with a warp density of 110 yarns / 2.5 cm and a weft density of 95 yarns / 2.5 cm was woven. This taffeta was subjected to scouring and dyeing (using Kayanol Blue NR 1% o.w., manufactured by Nippon Kayaku Co., Ltd.) by a conventional method, and then Asahi Guard AG as an emulsion type fluorinated water repellent. -7000 (Asahi Glass Co., Ltd.) is 6%, Sumitex Resin M-3 is 0.3% as a melamine resin, and Sumitex Accelerator is 0.1% (both from Sumika Chemtex Co., Ltd.) as a melamine resin catalyst. It was padded with an aqueous dispersion (squeezing ratio 30%), dried, and then heat treated at 170 ° C. for 1 minute.
Next, using a calendar processing machine having a mirror surface roll, crushing was performed under conditions of a temperature of 170 ° C., a pressure of 300 kPa, and a speed of 30 m / min to prepare a fabric used in this example.

[Preparation of synthetic resin solution]
On the other hand, a synthetic resin solution having the composition shown in Formula 1 below was prepared. The viscosity of this synthetic resin solution was 3000 mPa · s at 25 ° C.
<Prescription 1>
Heimlen Y-128NS 100 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution having a resin solid content of 25%)
Resamine X cross-linking agent 1 part by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., isocyanate compound)
3 parts by mass of Microsphere H755D (manufactured by Dainichi Seika Kogyo Co., Ltd., thermal expansion microcapsules with an average particle size of about 20 μm and a foaming temperature of 140 to 170 ° C.)
3 parts by mass of silica powder RA (B70) (manufactured by Fuji Silysia Chemical Ltd., hydrophilic and microporous silica fine powder obtained by gel method having an average particle diameter of about 70 μm)
Methyl ethyl ketone 15 parts by mass Toluene 15 parts by mass

[Preparation of polyurethane resin solution for barrier layer formation]
A polyurethane-based resin solution for forming a barrier layer having the composition shown in Formula 2 below was prepared. The viscosity of the resin solution was 5000 mPa · s at 25 ° C.
<Prescription 2>
Heimlen Y-128NS 100 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., solvent-type polyurethane resin solution having a resin solid content of 25%)
Resamine X cross-linking agent 1 part by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., isocyanate compound)
Methyl ethyl ketone 15 parts by mass Toluene 15 parts by mass Water 30 parts by mass

[Preparation of polyurethane resin solution for forming polyurethane microporous film]
A polyurethane-based resin solution for forming a polyurethane microporous film having the composition shown in Formula 3 below was prepared. The viscosity of this resin solution was 15000 mPa · s at 25 ° C.
<Prescription 3>
Rezamin CU4821 100 parts by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., ester-type polyurethane resin with 25% resin solids)
7 parts by mass of calcium carbonate (# 400) (manufactured by Nitto Flour Chemical Co., Ltd.)
Resamine X cross-linking agent 1 part by mass (manufactured by Dainichi Seika Kogyo Co., Ltd., isocyanate compound)
Dirac color L-1500 5 parts by mass (Dainippon Ink & Chemicals, white colorant)
N, N-dimethylformamide 30 parts by mass

[Formation of synthetic resin layer on one side of fabric]
The synthetic resin solution of formulation 1 was applied to the entire surface of one side (crushed surface) of the fabric at a coating amount of 120 g / m ² using a comma coater. And it dried on 120 degreeC conditions for 2 minutes, and formed the synthetic resin layer whose thickness is 25 micrometers.

[Formation of barrier layer on the surface of synthetic resin layer]
Subsequently, the polyurethane resin solution of Formula ² was applied to the entire surface of the synthetic resin layer formed as described above at a coating amount of 50 g / m ² using a floating knife coater. Then, the barrier layer having a thickness of 7 μm was formed by drying at 120 ° C. for 1 minute.

[Formation of polyurethane microporous film on the barrier layer surface]
Thereafter, the polyurethane resin solution of Formula 3 was applied to the entire surface of the barrier layer formed as described above at a coating amount of 120 g / m ² (dry resin coating amount of 30 g / m ² ) using a comma coater. Immediately, the polyurethane resin was solidified by immersing in 20 ° C. water for 1 minute. Then, after washing with hot water at 50 ° C. for 5 minutes and drying at 130 ° C. for 2 minutes, a polyurethane microporous film having a thickness of 55 μm was formed. The polyurethane microporous membrane had a microporosity of 55%.

[Formation of highly foamed layer]
A polyurethane microporous membrane was formed by wet coagulation, and then heated at 170 ° C. for 1 minute to expand the thermally expandable microcapsules present in the synthetic resin layer. A highly foamed fabric was obtained as described above.

Example 2
Except that the [formation of the synthetic resin layer on one side of the fabric] and the [formation of the barrier layer on the surface of the synthetic resin layer] were changed as follows, the moisture-permeable and waterproof highly foamed fabric was the same as in Example 1. Got.
[Formation of synthetic resin layer on one side of fabric]
The synthetic resin solution of Formula 1 was added to an 18 mesh gravure roll (dot shape; hemispherical, dot diameter; 0.75 mm, dot spacing; 0.65 mm, depth: 0.2 mm, dot occupation area ratio: about 20% ) At a coating amount of 30 g / m ^2, it was applied in a dot pattern on one side (crushed surface) of the fabric. And it dried on 120 degreeC conditions for 2 minutes. A synthetic resin layer having a thickness of about 40 μm was formed for each dot.
[Formation of barrier layer on the surface of synthetic resin layer]
The polyurethane resin solution of the formulation 2 was applied to the entire surface of the synthetic resin layer of the dot pattern formed above (also on the surface not provided with the dot pattern) at a coating amount of 20 g / m ² using a floating knife coater. Then, a barrier layer having a thickness of 3 μm was formed by drying at 120 ° C. for 2 minutes.

Comparative Example 1
A highly foamed fabric was obtained in the same manner as in Example 1 except that the silica powder RA (B70) in the formulation 1 was omitted.

Comparative Example 2
A highly foamed fabric was obtained in the same manner as in Example 1, except that the silica powder RA (B70) in the formulation 1 was removed and no barrier layer was formed.

The following items were evaluated for the moisture permeable and waterproof highly foamed fabrics obtained in Examples 1 and 2 and Comparative Examples 1 and 2 according to the following criteria. The results are shown in Table 1.
(1) Weight per unit (g / m ² )
The weight per unit m ² was measured.
(2) Thickness (μm)
Measurement was performed using a dial thickness gauge. In addition, the thickness of the highly foamed fabric of Example 2 measured the thickness of the location where the dot is provided.
(3) Sense of volume It was evaluated in the following three stages according to the value of thickness / weight per unit area.
○ ... Thickness / weight per unit area exceeds 2.0, and the volume feeling is very excellent.
Δ: Thickness / weight per unit area is 1.6 to 2.0, and has a slight volume feeling.
X: Thickness / weight per unit area is less than 1.6 and does not have a volume feeling.
(4) Texture In the handling (feel), the following three stages were evaluated.
○ ・ ・ ・ Soft.
Δ: Normal.
X ... Hard.
(5) Abrasion resistance Based on JISL-1084 and A-1 method, after friction of the polyurethane microporous membrane surface was repeated 100 times, the appearance was observed, and the wear durability was evaluated in the following three stages.
○: The surface of the microporous polyurethane membrane was slightly worn and damaged, and the wear resistance was almost good.
Δ: The degree of abrasion damage on the surface of the microporous polyurethane film is slightly strong.
X: Partial peeling occurred between the barrier layer and the microporous polyurethane membrane, and it was unsuitable as a moisture-permeable and waterproof highly foamed fabric.
(5) Three-dimensional effect and appearance feeling The three-dimensional effect and appearance feeling (visibility and clearness) were visually evaluated in the following three stages.
A: Three-dimensional appearance, visibility and sharpness were good.
○: The visibility and sharpness are good, but the stereoscopic effect is slightly inferior.
Δ: No three-dimensional appearance or appearance, and it was an ordinary synthetic resin film.

[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 Example 2 Comparative Example 1 Comparative Example 2
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Weight per unit area (g / m ² ) 146 122 144 136
Thickness (μm) 330 300 250 205
Sense of volume ○ ○ △ ×
(2.26) (2.46) (1.74) (1.51)
Texture ○ ○ △ ○ to △
Abrasion resistance ○ ○ ○ ○
Three-dimensional appearance and appearance △ ◎ △ △
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In addition, it was 152 kPa when the water-proof pressure was measured by the high water pressure method of JISL-1092 about the moisture-permeable waterproof high-foaming fabric which concerns on Example 2. FIG. Moreover, it was 6120 g / m < ² > * 24hrs when the water vapor transmission rate was measured by A-1 method of JISL-1099 description.

  As is clear from the results in Table 1, the highly foamed fabrics according to Examples 1 and 2 were superior to the highly foamed fabrics according to Comparative Examples 1 and 2 in terms of volume and texture. .

Claims (4)

Laminated and laminated in the order of polyurethane microporous membrane, barrier layer, highly foamed layer and fabric,
The polyurethane microporous membrane is obtained by wet coagulation of a polyurethane resin solution containing N, N-dimethylformamide as a main solvent,
The barrier layer is a polyurethane-based thin film layer that inhibits permeation of the N, N-dimethylformamide,
The highly foamed layer includes a thermally expanded microcapsule, a polyurethane resin for holding the microcapsule on one side of the fabric, and a hydrophilic and microporous material present on the surface of the microcapsule or in the polyurethane resin. A highly foamed fabric provided with a polyurethane microporous membrane, characterized in that it is made of a fine silica powder.   The highly foamed fabric according to claim 1, wherein the highly foamed layer is provided in a pattern on one side of the fabric. Applying a synthetic resin solution containing a thermally expandable microcapsule, a hydrophilic and microporous silica fine powder, and a polyurethane-based resin on one side of the fabric, and then drying to form a synthetic resin layer; ,
A step of laminating and laminating a polyurethane-based thin film layer that inhibits permeation of N, N-dimethylformamide on the surface of the synthetic resin layer to form a barrier layer composed of the polyurethane-based thin film layer;
Applying a polyurethane resin solution containing N, N-dimethylformamide as a main solvent to the barrier layer surface, and subsequently wet coagulating the polyurethane resin solution to form a polyurethane microporous film;
Then, the process of expanding the said thermally expansible microcapsule under heating comprises the manufacturing method of the highly foamed cloth provided with the polyurethane microporous film characterized by the above-mentioned.   The method for producing a highly foamed fabric according to claim 3, wherein the synthetic resin layer is provided in a pattern on one side of the fabric.