JPH053829B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Industrial Application] This invention relates to a moisture-permeable waterproof fabric suitable for various types of clothing such as raincoats, sports clothes, and dust-proof clothes, as well as for sports equipment such as tents, and upper material for footwear. The aim is to create a moisture-permeable waterproof fabric in the form of a porous film that has a high degree of moisture permeability and excellent wetting properties. (Prior art) Due to its usage, waterproof fabric-related materials allow moisture to pass through from the inside, but not water from the outside.
It is an extremely important factor to use a material that provides the user with as much comfort as possible, and various attempts have been made to put it into practical use. Among many of these trials, as an example of using porous films, U.S. Pat. Materials laminated with adhesive applied in lines or dots are disclosed. In addition, JP-A No. 59-158252 describes a ``waterproof material with excellent moisture permeability'' as described in the claims, ``a porous film that secures waterproofness and has moisture permeability. The first layer and the second layer, which is a woven or knitted fabric for reinforcing the first layer and providing necessary shape retention, are made of a hydrophilic material that contains a hydrophilic functional group and swells with moisture but does not dissolve. "Waterproof material with excellent moisture permeability characterized by being laminated with a polyurethane adhesive" is disclosed. In addition, JP-A-58-166036 describes, as a "novel waterproof and moisture permeable laminated fabric," as described in the claims, "(1) A microporous fabric whose main component is a polyurethane polymer. A film is attached to at least one side of a stretchable fiber material, and the elongation in the warp and weft directions is 5%.
A new bonded fabric characterized by having a water pressure resistance of 350 mmH ₂ O/cm ² and a moisture permeability of 2500 g/m ² /24 hrs or more. (2) A laminated fabric according to claim (1), characterized in that at least one side of the laminated fabric has a water repellency of 90 points or more. (3) A bonded fabric according to claim (2), characterized in that the opposite side of the water-repellent side has water absorbency with wicking properties of 100 seconds or less. ” A laminated fabric is disclosed. Furthermore, JP-A-59-140217, JP-A-59-
140219, PAU during solvent synthesis of polyamino acid urethane copolymer resin (PAU) having a polyamino acid segment and a polyurethane segment.
The film obtained by removing the solvent from the solution has moisture permeability,
It has particularly excellent breathability, and is suitable as a resin for artificial leather, as well as for waterproof fabrics coated on woven fabrics, non-woven fabrics, or porous substrates, and other textile processing applications. A method for producing urethane resin in a solvent mainly composed of dimethylformamide is shown. The above are conventional examples of porous film systems. Next, as an example of a non-porous film,
As disclosed in Publication No. 59-159338, the product name is Luxkin UX-678 [polyurethane resin manufactured by Seiko Kasei Co., Ltd.] or CRISVON 8006HV.
A moisture-permeable heat-retaining laminate material is disclosed in which a moisture-permeable film formed by adding aluminum powder to polyurethane resin (manufactured by Dainippon Ink Co., Ltd.) and bonded to a breathable fabric is bonded to a breathable fabric. As shown in the range, "Stretchable polyurethane that contains 0.5% or more of aluminum powder on one side of a fabric that is water repellent, breathable, and stretchable, and has a moisture permeability of 2000g/ ^m2・24hrs or more. JP-A No. 60-135245 discloses a laminate fabric of a non-porous film or A stretchable waterproof and moisture permeable fabric material is disclosed in which a direct coating fabric is interposed between stretchable fabrics in a bent state, and an adhesive portion is formed on the joint surface of the two.
As shown in the claims, ``a waterproof and moisture-permeable fabric is interposed between stretchable fabrics in a bent state, and an adhesive portion is formed on the joint surface of the stretchable fabric and the waterproof and moisture-permeable fabric. ``Stretchable waterproof and breathable fabric material'' is disclosed. In the above-mentioned conventional techniques, porous film-based fabrics have poor water pressure resistance, and their micropores become clogged with foreign matter during use, resulting in a gradual decrease in moisture permeability, making them unsuitable for use as waterproof fabrics. Therefore, non-porous films are preferred. [Problems to be solved by the invention] It is well known that polyoxyethylene glycol or a block copolymer of polyoxyethylene and polyoxypropylene is used as a polyol component as a means of imparting moisture permeability to a non-porous polyurethane film. It is being In the case of these conventional hydrophilic polyurethanes, when the polyoxyethylene content in the final polymer is increased to ensure the desired moisture permeability, the water absorption swelling property increases significantly, and the physical properties of the polymer layer when wet are deteriorated, making it impractical. I had a problem with my sexuality.
On the other hand, lowering the polyoxyethylene content improves the water absorption and swelling property, but this is not preferable because it lowers the moisture permeability. Furthermore, JP-A-60-6775 discloses a moisture permeable adhesive film using a non-porous film made of an ester polyurethane polymer.
Although this film avoids swelling when wet, its moisture permeability is 600 to 800 g m ² /24 hr.
Moisture permeability coefficient specified in JIS Z-0208 (1500g/ ^m2・
(24 hours or more) has not been obtained. Furthermore, various improvements have been made to the adhesives used to produce moisture-permeable waterproof fabrics by laminating these moisture-permeable films and base fabrics.
In particular, for adhesives with poor moisture permeability, spot-like or cotton-like partial adhesion has been adopted, but the adhesive area occupies 1/3 to 1/2 of the total effective surface area, which increases the moisture permeability. This results in loss of performance. Therefore, JP-A-59-158252 proposes laminating with a moisture-permeable adhesive, that is, a hydrophilic polyurethane adhesive containing a large amount of polyoxyethylene block. According to this, the moisture permeability is approximately twice as high as when using a commercially available thermoplastic urethane resin adhesive (all cases when the adhesive coverage is 50%), but the disadvantage is that it swells with moisture. There is. Furthermore, JP-A-60-6775 discloses a moisture-permeable adhesive film in which a pressure-sensitive adhesive composition prepared by adding a phenolic resin and a crosslinking agent to a millable type urethane elastomer is fully adhered to a non-porous polyurethane film. However, the moisture permeability of this adhesive film is 800 g/m ² ·24 hours, which is not sufficient. As mentioned above, as a polyol component, polyoxyethylene glycol can be used alone or in combination with polyoxypropylene glycol,
Non-porous moisture-permeable polyurethane films or adhesives using copolymers of both of them show a tendency for the swelling of the polymer due to water absorption to increase in proportion to the polyoxyethylene content, and when it swells, there is a significant decrease in strength. There is a drawback that it causes this, and the clothing is not suitable for use as a material for tents. Furthermore, ester polyurethane polymers developed as non-swellable materials have many problems such as insufficient moisture permeability. The moisture permeable waterproof fabric of the present invention solves the above problems. [Means for Solving the Problems] The present invention provides a breathable waterproof fabric in which a non-porous polyurethane film is bonded to at least one side of a breathable fabric via an adhesive.
The polyurethane film and adhesive each have a water absorption swelling rate of 5% or less and a moisture permeability coefficient of 2000 (g/m ²
The present invention relates to a moisture-permeable waterproof fabric with improved wetting properties made of a polyurethane composition having the following properties. The constituent material of the fabric used in this invention may be either natural fiber or synthetic fiber, and the form of the fabric may be made of these fibers alone or mixed with each other.
Woven fabrics, knitted fabrics, and non-woven fabrics formed by mixed weaving, mixed knitting, etc. can be used as long as they are breathable, but preferred examples include nylon plain weave, polyester/cotton blend plain weave, and various knit fabrics. Examples include abrasives, tricots, knits, etc. The moisture permeable polyurethane film used in this invention is non-porous and is made of a polyurethane composition with a water absorption swelling rate of 5% or less and a moisture permeability coefficient of 2000 g/m ² ·24 hr. or more. If available, polyurethane polymer films synthesized by other formulations can also be applied, but particularly preferred moisture-permeable polyurethane polymers include those with a molecular weight of 200.
~600 polyethylene glycol and organic dicarboxylic acid alone or a mixture of organic dicarboxylic acid and ε-caprolactone and/or short chain polyol are reacted to produce a polyoxyethylene content of 17 to 70%.
A polyurethane polymer is obtained by preparing a polyester polyol having a molecular weight of 500 to 3000, and reacting the polyester polyol with an organic polyisocyanate in the presence of a chain extender to have a polyoxyethylene content in the range of 15 to 62%. The composition is based on the composition, and weathering agents, pigments (coloring agents), and other compounding agents are appropriately added as necessary for practical purposes. Furthermore, the adhesive used in this invention is a polyurethane whose basic composition is the above non-porous, moisture-permeable polyurethane film polymer composition, with methoxymethylolated melamine and its curing catalyst added as additives. The adhesive is a moisture-permeable adhesive made of a polyurethane composition to which a softener, a weathering agent, a pigment, and other compounding agents are added as appropriate for practical use. The polyethylene glycol used in the composition of the polyester polyol is limited to a molecular weight in the range of 200 to 600 that provides a suitable moisture permeability coefficient and swelling rate. There are no restrictions on the organic dicarboxylic acid as long as it can undergo an esterification reaction with polyethylene glycol, but particularly preferred are adipic acid or isophthalic acid alone, or these dicarboxylic acids together with ε-caprolactone and/or 1,4-butane. It is a combination system of short-chain polyols such as diol, ethylene glycol, and propylene glycol, and the polyol that is the subject of this application obtained by reaction has a polyoxyethylene content of 17 to 70% by weight and a molecular weight of 500 to 3000. It is within the range of . In addition, organic polyisocyanates used for polyurethanizing polyester polyols include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI),
Isophorone diisocyanate (IPDI), hydrogenated MDI
Diisocyanates such as are preferred. For applications where discoloration is acceptable, use the well-known toluene diisocyanate (TDI), diphenylmethane-4,
4′-diisocyanate (MDI), crude (MDI), etc. can also be used. In addition, all known chain extenders can be used, such as polyethylene glycol,
diols such as neopentyl glycol,
4,4'-methylenebis(2-chloroaniline).
Examples include diamines such as isophorone diamine, piherazine, and ethylene diamine, and amino alcohols such as N-methylethanolamine and monoethanolamine. The moisture-permeable waterproof fabric of the present invention comprises the above-mentioned non-porous moisture-permeable polyurethane polymer film, a moisture-permeable adhesive, and fabrics, and is obtained by a direct coating method or a transfer coating method. In the transfer coating method, a non-porous polyurethane film formulation is applied to a release paper and dried, a moisture-permeable adhesive is applied to the surface of the film and dried, the fabric is crimped and laminated, rolled up, and placed in an oven. After aging for 24 hours, the release paper is peeled off to create a laminated cloth. If necessary, a treatment such as spray drying with a water repellent agent is performed. Note that details will be specifically explained in Examples. [Example] Next, an example of the structure of a polyester polyol and a polyurethane polymer will be shown. (a) Polyester polyol. Polyethylene glycol with a molecular weight of 200 [HO
(CH ₂ CH ₂ O) _o H] 1080 parts, adipic acid [HOO
(CH ₂ ) ₄ COOH] 642.4 parts and Tetrabutyl titanate [Ti(OC ₄ H ₉ ) ₄ ] was added at 0.001% based on the total amount of the composition to a composition consisting of 236 parts, and the mixture was heated to 200 to 210°C with stirring in a flask to perform an esterification reaction. The reaction was continued for 20 hours and dehydrated under reduced pressure to form a polyester polyol with a molecular weight of 1800. The polyoxyethylene content in the polyol determined by calculation is
It is 60%. (b) Polyurethane polymer. 100 parts of the above polyester polyol was reacted with 24 parts of isophorone diisocyanate to obtain an isocyanate-terminated prepolymer, and dimethylformamide [HCON(CH ₃ ) ₂ ] was added to this as a solvent.
(DMF) was added to give a solid content of 50%, and then 9 parts of isophoronediamine, a curing agent, was added to form a polyurethane polymer. The physical properties of a non-porous polyurethane film obtained from this polyurethane polymer solution by a casting method are shown in the following table.

[Table] (c) Composition of moisture-permeable adhesive based on polyurethane polymer. Polyester polyol 1 composed of the above (a)
1.9 moles of xylylene diisocyanate per mole are reacted to form a prepolymer having an isocyanate group at the end, methyl ethyl ketone is added to this to give a solid content of 50%, and then 1 mole of neopentyl glycol is added, A polyurethane polymer stock solution is prepared, and per 100 parts of this stock solution, 10 parts of methoxymethylolated melamine and 5 parts of an amine curing agent are added to constitute the basic composition solution of the moisture-permeable adhesive. This basic composition liquid may include softeners (e.g., Sumitex Softner S100, Sumitex Silicone Softner 10 and other plasticizers), weathering agents (e.g., various anti-aging agents), Pigments and other compounding agents are added as appropriate. In this example, in the above basic composition liquid,
An adhesive formulation was prepared by adding 1.5 parts of a softener, 3.5 parts of a weathering agent, and 45 parts of methyl ethyl ketone as a diluent. The solids content of this adhesive compound is 25%, and
The viscosity at is 4000cp. The properties of an adhesive film obtained from this adhesive mixture by a casting method are shown in the following table.

[Table] Polyurethane film with the above characteristic values,
The water absorption swelling rate and moisture permeability coefficient of an adhesive film are measured by forming a polyurethane polymer solution or an adhesive compound solution onto a glass plate using an applicator for film casting, and measuring the water absorption. In the case of swelling rate,
Form a film with a thickness of 20 μ x width 30 mm x length 150 mm, put marked lines on this film at 100 mm intervals, and after immersing it in water at room temperature for 24 hours, take it out of the water and immediately calculate the distance l between the marked lines. The measured value was calculated using the following formula as the water absorption swelling rate %. Water absorption swelling rate % = (l-100) x 100/100 In addition, in the case of moisture permeability coefficient, a film is similarly formed on a glass plate, and using this 20μ film, it is determined according to the regulations of JIS Z-0208. This is a measurement of the moisture permeability coefficient. (d) Composition of moisture-permeable waterproof fabric. Add 1 part of silicone surfactant and 45 parts of diluent (DMF) to 100 parts of polyurethane polymer solution to adjust the coating composition (viscosity
4300cp/10℃, solid content 35%) is coated with a coating device (e.g., comma coater) and placed on a release material such as release paper at a constant speed until the film thickness after drying is 20μ. The polyurethane film is coated continuously and passed through a drying oven for drying (drying conditions: 100°C x 1 minute), and the polyurethane film with the release paper still attached is transferred to a second coating device connected in series ( For example, a comma coater) and then apply adhesive mixture (viscosity
4000cp, solid content 25%) was applied continuously using a comma coater so that the thickness of the adhesive layer after drying was 20μ, and passed through a drying oven to dry (drying conditions 80℃ x 1 minute). Then, a fabric such as nylon taffeta (for example, pile fabric with a number of strokes of 85 x 105) is bonded and bonded to the adhesive film surface of the laminate sent out from the drying oven using a pressure roll. After that, it is wound onto a take-up roll, aged in an oven at 60°C for 24 hours, and then peeled off from the release paper (the release paper is used repeatedly). Thereafter, if necessary, the fabric surface is treated with a silicone water repellent or the like to form a moisture permeable waterproof fabric. This water-repellent treated moisture-permeable waterproof fabric has a moisture permeability coefficient of 3500 g/m ² 24H, a wet adhesive strength (between nylon taffeta adhesives) of 2 kg/2 cm or more, and a water absorption swelling rate =
0, Water pressure resistance of 20,000mm water column or more (according to JIS L-1092 regulations), Scotto type rubbing resistance test (wet) 2000
(load 1 kg) or more (according to the regulations of JIS L-1041). As mentioned above, the adhesive of the present invention can obtain sufficient moisture permeability and adhesive strength by bonding the entire surface, but it is also possible to use partial bonding in the form of dots or lines as the case may be. Next, Table 3 (fabric composition and physical properties) shows the physical properties of each sample depending on the type of base fabric of the moisture-permeable waterproof fabric and the difference in the total thickness of the polyurethane film and adhesive film. Sample No. 1 is from the above example.

[Action/effect of the invention]

The polyurethane film constituting the moisture-permeable waterproof fabric of this invention is non-porous and has excellent physical properties, so there is no risk of tearing when the film is peeled off from the release paper when constructing the moisture-permeable waterproof fabric. It is possible to make the film extremely thin, the water absorption swelling rate is virtually zero, and the deterioration of physical properties due to swelling when wet is suppressed, so even films with a thickness of 15 to 20 μm can be used in practical applications. It will be done. The ability to reduce the thickness in this manner is also favorable for moisture permeability. Further, even when water droplets adhere to a part of the film surface, no partial blistering phenomenon is observed, and the film exhibits its properties as a waterproof cloth. In particular, the moisture permeability coefficient measured for the 20μ product was 4500.
It exhibits extremely good moisture permeability of g/m ²・24H. Regarding adhesives, fabrics not only have excellent adhesive strength (especially when wet) and physical properties that will not peel or tear when rubbed or washed, but also have excellent moisture permeability. It is something that demonstrates the. In addition, especially when the water absorption swelling rate is zero, it is possible to obtain a durability effect that exhibits suitable adhesive fabric characteristics for a long period of time without reducing adhesive strength. As described above, the present invention provides a moisture permeable fabric with improved moisture properties in a well-balanced manner, including moisture permeability, wet adhesive strength, water absorption swelling property, water pressure resistance, and wet rubbing resistance among the various properties necessary for a moisture permeable fabric. A waterproof fabric may be provided. In addition, for this moisture-permeable fabric, depending on the application and processing form of the fabric, in addition to full-surface bonding, partial bonding such as dotted or linear bonding can be appropriately selected and used.

Claims (1)

[Scope of Claims] 1. A moisture-permeable waterproof fabric in which a non-porous polyurethane film is bonded to at least one side of the fabric via an adhesive, wherein each of the polyurethane film and the adhesive has a water absorption swelling rate of 5%. Below,
A moisture-permeable waterproof fabric with improved moisture characteristics, characterized by being made of a polyurethane composition having a moisture permeability coefficient of 2000 (g/m ² ·24H) or more. 2 The non-porous polyurethane film has a molecular weight
200 to 600 polyethylene glycol and organic dicarboxylic acid alone or a mixture of organic dicarboxylic acid and ε-caprolactone and/or short chain polyol are reacted to obtain a polyoxyethylene content of 17 to 70
% and has a molecular weight of 500 to 3000, and the polyester polyol is reacted with an organic polyisocyanate in the presence of a chain extender to have a polyoxyethylene content in the range of 15 to 62%. Claim 1 is characterized by having a type polyurethane polymer composition, and if necessary, weathering agents, pigments, and other compounding agents are added as appropriate.
A moisture-permeable waterproof fabric with improved wetting properties as described in Section 1. 3 The thickness of the non-porous polyurethane film is 10
A moisture-permeable waterproof fabric with improved wetting properties as claimed in claim 1, which has a particle diameter of 25μ. 4. The adhesive is added as an additive to the polymer composition for non-porous polyurethane film according to claim 2.
A polyurethane adhesive whose basic composition is methoxymethylolated melamine and its curing catalyst, and a moisture-permeable adhesive to which softeners, weathering agents, pigments, and other compounding agents are added as needed. A moisture permeable waterproof fabric with improved wetting properties as claimed in claim 1.