CN113498915B - Waterproof slide fastener and method for manufacturing waterproof slide fastener - Google Patents
Waterproof slide fastener and method for manufacturing waterproof slide fastener Download PDFInfo
- Publication number
- CN113498915B CN113498915B CN202110800451.3A CN202110800451A CN113498915B CN 113498915 B CN113498915 B CN 113498915B CN 202110800451 A CN202110800451 A CN 202110800451A CN 113498915 B CN113498915 B CN 113498915B
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- fastener
- reactive hot
- melt adhesive
- manufacturing
- slide fastener
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B19/00—Slide fasteners
- A44B19/24—Details
- A44B19/32—Means for making slide fasteners gas or watertight
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B19/00—Slide fasteners
- A44B19/24—Details
- A44B19/34—Stringer tapes; Flaps secured to stringers for covering the interlocking members
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B19/00—Slide fasteners
- A44B19/42—Making by processes not fully provided for in one other class, e.g. B21D53/50, B21F45/18, B22D17/16, B29D5/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1207—Heat-activated adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1207—Heat-activated adhesive
- B32B2037/1215—Hot-melt adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
- B32B2037/1261—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive moisture curable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Slide Fasteners (AREA)
Abstract
Provided is a waterproof slide fastener which is improved in environmental load and heat resistance. The slide fastener has a pair of right and left fastener stringers including a fastener tape and a fastener element row attached to a side edge of the fastener tape, the fastener tape including a base fabric and a water-stop film attached to at least one side surface of the base fabric, the water-stop film having a laminated structure including a surface layer and an adhesive layer of a cured body of a reactive hot melt adhesive adjacent to the surface layer.
Description
Technical Field
The present invention relates to a waterproof slide fastener. The present invention also relates to a method for manufacturing a waterproof slide fastener.
Background
Slide fasteners are widely used as opening and closing tools for articles of daily use such as clothing, bags, shoes, and sundry goods, and are also used for protective clothing such as space wear, chemical protective clothing, diving suits, and life boats, covers for transport containers, and tents. In the special applications as described above, the slide fastener is required to be waterproof.
Slide fasteners are generally composed mainly of the following three parts: a pair of elongated fastener tapes, fastener elements which are engagement portions of a fastener attached by sewing along one side edge of each tape, and a slider for controlling opening and closing of the fastener by engaging and disengaging the fastener elements. In order to impart water repellency to a slide fastener, a slide fastener is known in the prior art in which synthetic resin films having water repellency are adhered to fastener tapes, and the synthetic resin films of the right and left fastener tapes are brought into close contact with each other at the time of engagement to thereby exert water repellency. As the synthetic resin film, a polyurethane film is known.
WO2014/010019 (patent document 1) discloses a method of adhering a polyurethane film to a fastener tape using an aqueous polyurethane adhesive. Japanese patent No. 5213523 (patent document 2) discloses a method of covering a fastener tape with a polyurethane film via an inner layer formed of a polyurethane adhesive, an adhesive or a hot melt adhesive.
[ Prior Art ]
[ patent literature ]
[ patent document 1]: WO2014/010019
[ patent document 2]: japanese patent No. 5213523
Disclosure of Invention
[ problem to be solved by the invention ]
The technique described in WO2014/010019 takes environmental load into account, and the effort in this respect is worth affirming using water as the dispersion medium for the adhesive. However, there is a problem in that it takes a long time to dry the adhesive. On the other hand, japanese patent No. 5213523 discloses a hot melt adhesive. The hot melt adhesive is a solvent-free adhesive, so that the problem of drying time can be overcome. However, the hot melt adhesive has a problem in heat resistance due to the use of a thermoplastic resin.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a waterproof slide fastener having improved environmental load and heat resistance. Another object of the present invention is to provide a method for manufacturing such a waterproof slide fastener.
[ means for solving the problems ]
The waterproof slide fastener according to the present invention includes a pair of left and right fastener stringers including a fastener tape and a fastener row attached to a side edge of the fastener tape, wherein the fastener tape includes a base fabric and a water-stop film attached to at least one side surface of the base fabric, and the water-stop film has a laminated structure including a surface layer and an adhesive layer of a cured body of a reactive hot-melt adhesive adjacent to the surface layer.
Another aspect of the present invention is a method for manufacturing a waterproof slide fastener, comprising: a step of performing a method of manufacturing a fastener tape and manufacturing a pair of the fastener tapes; a step of manufacturing fastener stringers by attaching fastener element rows to side edges of each of the manufactured fastener stringers; and a step of attaching a slider between the left and right element rows of the pair of fastener stringers, wherein the fastener stringer manufacturing method comprises: bonding the surface layer to the base fabric with a reactive hot-melt adhesive; and a step of moisture-curing the reactive hot-melt adhesive.
Further, another aspect of the present invention is a method for manufacturing a waterproof slide fastener, comprising: a step of performing a method of manufacturing a fastener tape and manufacturing a pair of the fastener tapes; a step of manufacturing fastener stringers by attaching fastener element rows to side edges of each of the manufactured fastener stringers; and a step of attaching a slider between the left and right element rows of the pair of fastener stringers, wherein the fastener stringer manufacturing method comprises: a step of sequentially laminating or simultaneously laminating a reactive hot-melt adhesive for an adhesive layer and a reactive hot-melt adhesive for a surface layer on a base fabric; and a step of moisture-curing the reactive hot-melt adhesive for the adhesive layer and the reactive hot-melt adhesive for the surface layer together.
[ Effect of the invention ]
The reactive hot melt adhesive used in the present invention is solvent-free, has a small environmental load, and is excellent in heat resistance. In addition, since the reactivity and the handling property are excellent, the productivity of the waterproof fastener tape is improved. Therefore, according to the present invention, it is possible to provide a waterproof slide fastener having improved environmental load and heat resistance.
Drawings
Fig. 1 is a schematic view showing a laminated structure of a fastener tape of a slide fastener according to a first embodiment of the present invention.
Fig. 2 is a schematic view showing a laminated structure of a fastener tape of a slide fastener according to a second embodiment of the present invention.
Fig. 3 is a top view of a zipper according to an embodiment of the invention.
Fig. 4 is a cross-sectional view of a slide fastener according to an embodiment of the invention.
Fig. 5 is a perspective cross-sectional view of a slide fastener according to an embodiment of the present invention.
Fig. 6 is a perspective view of a fastener stringer constituting a slide fastener according to another embodiment of the present invention.
Fig. 7 is a cross-sectional view of the zipper of fig. 6.
[ description of the reference numerals ]
10a, 10b: a fastener tape; 11: a base cloth; 12: a water-stopping film; 12a: a multi-layer water-stop film; 12b: a single-layer water-stopping film; 13: a surface layer; 14: an adhesive layer; 20: waterproof zippers; 21: a fastener element row; 22: a pull head; 23: a core wire; 24: a sewing thread; 25: a pull tab; 26: an upper stopper; 27: a fastener stringer; 28: zipper teeth; 29: a pull head; 30: a fastener tape; 31: a core; 32: a base cloth; 33: and (5) a water-stopping film.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Fig. 1 shows a laminated structure of fastener tapes of a slide fastener according to a first embodiment of the present invention. The fastener tape 10a includes a base fabric 11 and a multilayer water-blocking film 12a attached to at least one surface of the base fabric 11. The multilayer water-blocking film 12a includes a surface layer 13 made of a polyurethane urea film, and an adhesive layer 14 made of polyurethane urea adjacent to the surface layer 13. The adhesive layer 14 is a cured body of a reactive hot melt adhesive. Specifically, the fastener tape 10a includes an adhesive layer 14 on the base fabric 11 side of the top sheet 13, and the adhesive layer 14 is adhered between the base fabric 11 and the top sheet 13. In this way, the fastener tape 10a has a laminated structure in which the top sheet 13, the adhesive layer 14, and the base fabric 11 are laminated in this order from the upper side of the paper surface in fig. 1.
Fig. 2 shows a laminated structure of fastener tapes of a slide fastener according to a second embodiment of the present invention. The fastener tape 10b includes a base fabric 11 and a single-layer water-blocking film 12b made of polyurethaneurea adhered to at least one surface of the base fabric 11. The single-layer water-blocking film 12b is a cured body of the reactive hot-melt adhesive, and is in direct contact with the base fabric 11. That is, the single-layer water-blocking film 12b in the fastener tape 10b serves as both the top sheet 13 and the adhesive layer 14 in the first embodiment. In this way, the fastener tape 10b has a laminated structure in which the single-layer water stop film 12b and the base fabric 11 are laminated in this order from the upper side of the drawing sheet of fig. 2.
(1. Base cloth)
The material of the base fabric 11 may be natural fibers or synthetic fibers commonly used in fastener tapes, and is not particularly limited, and examples thereof include polyamide fibers, polyester fibers, and acrylic fibers. The base fabric 11 can be produced by weaving or braiding these synthetic fibers. Typically, polyester fibers may be used for weaving or braiding.
(2. Adhesive layer and Single layer Water-stop film)
The polyurethane urea constituting the adhesive layer 14 in the first embodiment and the single-layer water-blocking film 12b in the second embodiment is one or more polyurethane ureas selected from the group consisting of polycarbonate polyurethane urea, polycarbonate polyether polyurethane urea, polycarbonate polyester polyurethane urea, and polycarbonate polyether polyester polyurethane urea. In addition to hydrolysis resistance, heat resistance and shuttle durability, the polyurethane urea is preferably one or more polyurethane ureas selected from the group consisting of polycarbonate polyether polyurethane urea and polycarbonate polyether polyester polyurethane urea from the viewpoint of improving flexibility, and is more preferably polycarbonate polyether polyester polyurethane urea from the viewpoint of improving the overall balance of hydrolysis resistance, heat resistance, shuttle durability and flexibility.
The polyurethaneurea constituting the adhesive layer 14 in the first embodiment and the single-layer water-blocking film 12b in the second embodiment has urethane groups (-NHCOO-) and urea groups (-NHCONH-) at bonding sites between polymer units. The urethane urea has urethane groups and urea groups in a predetermined ratio, which will be described later in detail, contributes to a balance among water repellency, strength, weather resistance, abrasion resistance, appearance, and flexibility suitable for a fastener tape.
The polycarbonate-based polyurethaneurea is a polymer having a moiety bonded to each other through an urea group and a moiety bonded to each other through a urethane group. The polycarbonate-polyether polyurethaneurea refers to a copolymer of polycarbonate urethane and polyether urethane, typically a block copolymer, and refers to a copolymer having a portion bonded between polymer units through urea groups and a portion bonded between polymer units through urethane groups. The polycarbonate-polyester polyurethaneurea refers to a copolymer of polycarbonate urethane and polyester urethane, typically a block copolymer, and refers to a copolymer having a portion bonded between polymer units through urea groups and a portion bonded between polymer units through urethane groups. The polycarbonate-polyether-polyester polyurethaneurea refers to a copolymer of polycarbonate urethane, polyether urethane and polyester urethane, typically a block copolymer, and refers to a copolymer having a portion bonded between polymer units through urea groups and a portion bonded between polymer units through urethane groups.
As described previously, when the polyurethaneurea constituting the adhesive layer 14 and the single-layer water-stop film 12b in the first embodiment has urethane groups (-NHCOO-) and urea groups (-NHCONH-) the molar ratio of the two of the polyurethaneurea affects the characteristics of the adhesive layer 14 and the single-layer water-stop film 12b, handling operability before curing the adhesive layer 14 and the single-layer water-stop film 12b, and reactivity. When the molar ratio of the urea group to the urethane group in the polyurethaneurea becomes too low, in other words, the molar ratio of the isocyanate group (-NCO) to the urethane group (-NHCOO-) in the reactive hot-melt adhesive before curing becomes too low, the viscosity increases together with the molecular weight of the prepolymer, and the handling operability deteriorates. In particular, the material replenishment takes a longer time or becomes less coatable. In contrast, when the molar ratio of the urea group to the urethane group in the polyurethaneurea becomes high, in other words, the molar ratio of the isocyanate group (-NCO) to the urethane group (-NHCOO-) in the reactive hot-melt adhesive before curing becomes high, the curing reaction can be promoted, and the functions of water resistance, corrosion resistance, abrasion resistance, and the like, which are characteristics of polyurea, can be improved. Therefore, the molar fraction of the urea groups is preferably 0.1 or more, more preferably 0.2 or more, when the total molar fraction of the urethane groups and urea groups in the polyurethaneurea is 1.
However, when the molar ratio of the urea group to the urethane group in the polyurethaneurea becomes too high, in other words, the molar ratio of the isocyanate group (-NCO) to the urethane group (-NHCOO-) in the reactive hot-melt adhesive before curing becomes too high, the foaming amount becomes large at the time of curing to deteriorate the beauty, or the flexibility of the resulting polyurethaneurea is easily impaired. Therefore, the molar fraction of the urea groups is preferably 0.5 or less, more preferably 0.4 or less, when the total molar fraction of the urethane groups and urea groups in the polyurethaneurea is 1.
The mole fraction of ureido groups in the polyurethaneurea can be obtained by using an NMR measuring device 13 C-NMR spectrum and analysis thereof. Specifically, 50 to 100mg (weight below this range may be the case) of the water-stop film or the adhesive layer is cut out, and the obtained material is prepared as a sample and set in an NMR measurement apparatus for measurement. The measurement conditions were as follows.
And (3) measuring a core: 13 C
resonance frequency: 500MHz
Cumulative number of times: 252 times
Measuring temperature: 25 DEG C
Assay: DDMAS method
The above-mentioned cumulative number of times; can judge the minimum value of the wave crest
(3. Surface layer)
In the first embodiment, the polyurethane urea constituting the surface layer 13 may be polyurethane urea capable of constituting the adhesive layer 14, or another polyurethane urea may be used. Therefore, the polyurethaneurea constituting the surface layer 13 may be one or more polyurethaneureas selected from the group consisting of polycarbonate-polyether-based polyurethaneurea, polycarbonate-polyester-based polyurethaneurea, and polycarbonate-polyether-polyester-based polyurethaneurea, as in the case of the adhesive layer 14. The polyurethaneurea constituting the surface layer 13 may have the same composition as the polyurethaneurea constituting the adhesive layer 14, or may have a different composition. However, the surface layer 13 is particularly important for mechanical strength and hydrolysis resistance, and a polycarbonate-based polyurethaneurea may be used. The polycarbonate-based polyurethaneurea is a polymer having a moiety bonded between terminals of polycarbonate through an ureido group and a moiety bonded between terminals of polycarbonate through a urethane group.
(4. Thickness of water stop film)
If the thickness of the water-blocking films 12a, 12b is too small, the feel is impaired, and therefore, it is preferably 0.07mm or more, more preferably 0.10mm or more. On the other hand, if the thicknesses of the water stop films 12a, 12b are too thick, the slider will be in sliding contact during opening and closing of the slide fastener, and thus the sliding property will be impaired, and it is preferably 0.25mm or less, more preferably 0.20mm or less.
(5. Method for producing fastener tape)
The method of manufacturing the fastener tape of the present invention will be described by way of example only.
In one embodiment of the method for producing a fastener tape of the present invention, the method comprises: bonding a surface layer formed of a polyurethane urea film to a base fabric by means of a reactive hot-melt adhesive; and a step of moisture-curing the reactive hot-melt adhesive. The method is a method for manufacturing a water-blocking film comprising a plurality of layers of an adhesive layer and a surface layer.
In another embodiment of the method for producing a fastener tape of the present invention, the method comprises: a step of sequentially or simultaneously laminating the reactive hot-melt adhesive for the adhesive layer and the reactive hot-melt adhesive for the surface layer on the base fabric in this order; and a step of moisture-curing the reactive hot-melt adhesive for the adhesive layer together with the reactive hot-melt adhesive for the surface layer. The method is a method for manufacturing a water-blocking film comprising a plurality of layers of an adhesive layer and a surface layer.
In still another embodiment of the method for producing a fastener tape of the present invention, the method includes: coating a reactive hot-melt adhesive on the base fabric; and a step of moisture-curing the reactive hot-melt adhesive.
The reactive hot melt adhesive may be coated on the base fabric by a coating method well known in the art such as roll coating, die coating, bead coating, and spray coating. The reactive hot-melt adhesive is usually applied to the base fabric in a heated state, and is preferably applied by heating to 130 ℃ or less, more preferably to 120 ℃ or less, in order to prevent the stability of the adhesive from decreasing, and is also useful for base fabrics having low heat resistance. In addition, from the viewpoint of improving the fluidity and workability of the adhesive, it is preferable to heat to 100 ℃ or higher for coating, and it is more preferable to heat to 110 ℃ or higher for coating.
In order to facilitate the application at the above temperature, the melt viscosity of the reactive hot-melt adhesive is preferably 5pa·s/120 to 50pa·s/120 ℃, more preferably 7pa·s/120 to 30pa·s/120 ℃. The melt viscosity of the reactive hot melt adhesive can be measured under the following conditions.
The device comprises: cone plate viscometer (ICI system) 20P cone
Temperature conditions: 120 DEG C
The melting temperature of the reactive hot-melt adhesive is preferably 40 to 100 ℃, more preferably 50 to 90 ℃. The melting temperature of the reactive hot melt adhesive means a temperature obtained by the method according to JIS K7121:2012, by DSC (differential scanning calorimeter).
In any of the above embodiments, the reactive hot melt adhesive preferably contains, as a main component, at least one prepolymer selected from the group consisting of a polycarbonate-based isocyanate-terminated urethane prepolymer, a polycarbonate-polyether-based isocyanate-terminated urethane prepolymer, a polycarbonate-polyester-based isocyanate-terminated urethane prepolymer, and a polycarbonate-polyether-polyester-based isocyanate-terminated urethane prepolymer, and has a urethane group and an isocyanate group such that the molar ratio of the isocyanate group to the urethane group is 0.5 to 1.5.
This is because of the following reason. Consider the following: reacting the hydroxyl groups of Amol with Bmol of isocyanate groups to give a terminal isocyanate-based urethane prepolymer, and moisture curing the prepolymer to give a polyurethaneurea. If B > A is used, the urethane group of Amol is formed by the reaction of the hydroxyl group with the isocyanate group, and (B-A) mol of the isocyanate group remains. The isocyanate groups react with moisture in the air to form carbamic acid, and they release carbon dioxide to form amines, and the amines react with other isocyanate groups to form urea groups. That is, one ureido group is formed from two isocyanate groups by the following reaction, and thus the resultant ureido group is (B-A)/2 mol.
R-NCO+H 2 O→R-NHCOOH→R-NH 2 +CO 2 (R is an organic group)
R-NH 2 +R-NCO→RNHCONHR
Therefore, if the molar ratio of isocyanate groups to hydroxyl groups before the urethane prepolymer is formed is not sufficiently high, the amount of urea groups formed does not increase. When the molar ratio of isocyanate groups to hydroxyl groups is less than 1.5 (in other words, the molar ratio of isocyanate groups to urethane groups in the isocyanate group-terminated urethane prepolymer is less than 0.5), the molecular weight (viscosity) of the urethane prepolymer becomes very large and sufficient urea groups are not formed. In this case, the handling operability is deteriorated, and the reactivity (moisture curing) is impaired because the isocyanate group is small. Therefore, the molar ratio of isocyanate groups to hydroxyl groups before the urethane prepolymer is formed is preferably 1.5 or more, more preferably 1.7 or more. In other words, the molar ratio of isocyanate groups to urethane groups in the isocyanate group-terminated urethane prepolymer is preferably 0.5 or more, more preferably 0.7 or more. On the other hand, when the molar ratio of the isocyanate groups to the hydroxyl groups before the formation of the urethane prepolymer exceeds 2.5 (in other words, the molar ratio of the isocyanate groups in the isocyanate group-terminated urethane prepolymer to the urethane groups exceeds 1.5), foaming becomes large at the time of curing to impair the beauty, or the cured body becomes too hard to impair the flexibility. Therefore, the molar ratio of isocyanate groups to hydroxyl groups before the urethane prepolymer is formed is preferably 2.5 or less, more preferably 2.3 or less. In other words, the molar ratio of isocyanate groups to urethane groups in the isocyanate group-terminated urethane prepolymer is preferably 1.5 or less, more preferably 1.3 or less.
Moisture curing of the reactive hot melt adhesive is performed at room temperature. Therefore, heating energy can be reduced. If moisture curing progresses with time (for example, about 24 hours), urea bonds are formed, and further biuret bonds, allophanate bonds, and the like are also formed, and the three-dimensional crosslinked structure is developed (cured). Thus, a waterproof film is adhered or formed on the base fabric, and a fastener tape having waterproof performance is obtained. However, quantitative analysis of three-dimensional crosslinking is difficult and, because of the trace amount, is not an object of discussion in the present invention.
(6. Embodiment of slide fastener)
Fig. 3 to 5 show an example of a waterproof slide fastener 20 having a fastener tape according to the present invention. Fig. 3 is a plan view of the entire waterproof slide fastener 20, fig. 4 is a cross-sectional view showing a state in which the element rows 21 are engaged in the slider 22, and fig. 5 is a partial perspective cross-sectional view of the waterproof slide fastener 20. The linear type coil fastener element rows 21 having the core thread 23 inserted therein are sewn and attached to one side surface of the base fabric 11 of each fastener tape 10 along the side edges thereof by sewing threads 24 of a double circular seam of a sewing machine. The coil-shaped fastener element row 21 may be formed of monofilaments of synthetic resin such as polyamide and polyester. The water stop films 12 of the pair of fastener tapes 10 may be bonded to the blanks of the article by means of an adhesive. As another method, the water-blocking film 12 and the blank may be welded by high frequency welding, or may be sewn and attached. A slider is inserted between the left and right element rows, and the slider is slid, whereby the open/close state of the slide fastener can be controlled. The sewing thread 24 may be subjected to a waterproof process.
By projecting the water-stop film 12 on the side of the engagement center line a of the element row with respect to the side edge of the base cloth 11, adhesion between the left and right water-stop films 12 is facilitated, and the waterproof property is improved. When the side edges of the water stop film 12 are made to protrude slightly beyond the engagement center line a of the element rows, the water stop films 12 are closely adhered to each other when the left and right element rows are engaged, and thus, higher water resistance can be obtained.
When the slide fastener 20 of the present embodiment is used, it is preferable that the side to which the water stop film 12 is attached be the outer surface, and the fastener element row 21 side be the inner surface, and be attached to the adherend. The pull tab 25 of the pull head 22 may be mounted on the outer surface side. As shown in fig. 3, an upper stopper 26 may be provided, and although not shown, a lower stopper, a separable insert, and the like may be attached.
Fig. 6 and 7 are partial schematic views of a waterproof slide fastener according to another embodiment of the present invention. Specifically, fig. 6 is a cross-sectional view schematically showing a state in which right and left fastener elements 28 are engaged with each other inside a slider 29 in the slide fastener according to the present embodiment, and fig. 7 is a part of a fastener stringer 27 constituting the waterproof slide fastener according to the present embodiment.
In the present embodiment, as shown in fig. 6 and 7, the fastener element 28 is injection molded so as to sandwich the entire core portion 31 formed at the end edge of the fastener tape 30 from the front and back surfaces. The slider 29 is shown at an imaginary line shown by a chain line. The fastener tape 30 is formed by attaching a water-blocking film 33 to the outer surface of the base fabric 32. As shown in fig. 7, the front end of the fastener element 28 on the one hand (the end facing the fastener tape on the other hand) is brought into close contact with the fastener tape 30 on the other hand at the time of engagement, whereby the waterproof property is exhibited.
Examples
(1. Preparation of reactive Hot melt adhesive)
Example 1
A reactive hot melt adhesive of the following specifications was prepared, which comprises a polycarbonate-polyether-polyester isocyanate-terminated urethane prepolymer as a main component.
DIC Co., ltd., product number: tyforce NH-470
Melt viscosity: 15 Pa.s/120 DEG C
Example 2
A reactive hot melt adhesive of the following specifications was prepared, which contains a polycarbonate-based isocyanate group-terminated urethane prepolymer as a main component.
DIC Co., ltd., product number: tyforce NH-460
Melt viscosity: 20 Pa.s/120 DEG C
Example 3
A reactive hot melt adhesive of the following specifications was prepared, which comprises a polycarbonate/polyether isocyanate group-terminated urethane prepolymer as a main component.
DIC Co., ltd., product number: tyforce NH-480
Melt viscosity: 10 Pa.s/120 DEG C
Example 4
A reactive hot melt adhesive of the following specifications was prepared, which comprises a polycarbonate/polyester-based isocyanate group-terminated urethane prepolymer as a main component.
DIC Co., ltd., product number: tyforce NH-490
Melt viscosity: 15 Pa.s/120 DEG C
Comparative example 1
A reactive hot melt adhesive of the following specification was prepared, which comprises a polyether-polyester isocyanate group-terminated urethane prepolymer as a main component.
DIC Co., ltd., product number: tyforce NH-410
Melt viscosity: 15 Pa.s/120 DEG C
Comparative example 2
A reactive hot melt adhesive of the following specifications was prepared, which comprises a polycarbonate-polyether-polyester isocyanate-terminated urethane prepolymer as a main component.
DIC Co., ltd., product number: tyforceNH-430
Melt viscosity: 5 Pa.s/120 DEG C
Comparative example 3
A reactive hot melt adhesive of the following specifications was prepared, which comprises a polycarbonate-polyether-polyester isocyanate-terminated urethane prepolymer as a main component.
DIC Co., ltd., product number: tyforceNH-450
Melt viscosity: 20 Pa.s/120 DEG C
The melt viscosity of the reactive hot melt adhesive was measured under the above-described measurement conditions using a cone-plate viscometer (ICI) 20P cone.
(2. Manufacture of waterproof slide fastener)
Each of the reactive hot-melt adhesives prepared above was melted by heating, and continuously and simultaneously laminated on a long release paper with a coating width of 180mm using a coating apparatus under a thickness of 10m/min and 150 μm. Next, the obtained laminate of the release paper-adhesive layer was adhered to the surface of a fastener tape sewn with polyester threads of a nylon fastener, and heated at 80 ℃ for 60 seconds, and after that, after moisture curing at room temperature for 24 hours or more, the release paper was peeled off, thereby producing each sample of the waterproof fastener tape having a water-stop film composed of a single-layer structure of a polyurethaneurea-based film. By attaching a fastener element and a slider to each sample of the waterproof fastener tape, a waterproof fastener having the structure shown in fig. 3 to 5 is manufactured.
(3. Mole fraction of ureido groups)
The respective water-blocking films were obtained by using an NMR measuring apparatus (model JNX-ECX500 manufactured by Japanese electric Co., ltd.) under the above-mentioned measuring conditions 13 The molar fraction of the urea groups was determined by analyzing the C-NMR spectrum and assuming that the total molar fraction of the urethane groups and urea groups was 1. The sample was selected by cutting with scissors. 13 In the C-NMR spectrum, peaks in the range of 150 to 154ppm correspond to urea groups and peaks in the range of 155 to 160ppm correspond to urethane groups, and the mole fraction was determined by the area ratio. The results are shown in Table 1.
(4. Hydrolysis resistance test)
Each waterproof slide fastener was placed in a constant temperature and humidity tank at 70 ℃ and 95% relative humidity, and an exposure test was performed for a certain period of time. For the waterproof slide fastener after the exposure test, a reciprocating open/close endurance test accompanied by 100 times of open/close was performed in M-level according to JIS S3015 (2007), and the state of peeling of the water-blocking film was visually checked. The evaluation was performed based on the following criteria. The results are shown in Table 1.
After =9 weeks, the film peeled less than 1mm 2
After o=5 weeks, the film peeled offApart from less than 1mm 2
After x=5 weeks, the film peeled off to 1mm 2 Above mentioned
(5. Test of durability of opening and closing)
For the waterproof slide fastener, a reciprocating open/close endurance test accompanied by 500 times of open/close was performed in M-level according to JIS S3015 (2007), and the state of peeling of the water-blocking film was visually checked. The evaluation was performed based on the following criteria. The results are shown in Table 1.
O = film peel less than 1mm 2
X = film peel 1mm 2 Above mentioned
(6. Appearance (foaming resistance))
The appearance of the water-blocking film was visually observed, whereby the foaming was visually inspected, and evaluated based on the following criteria. The results are shown in Table 1.
O = no change in appearance due to foaming
X=appearance change due to foaming
(7. Heat resistance test)
For the waterproof slide fastener, the water-stop film after heating at 120 ℃ for 6 hours was visually inspected for cloudiness, and evaluated based on the following criteria. The results are shown in Table 1.
O = no white turbidity at all
Delta=a part of which has white turbidity
X = all white turbidity
(8. Softness test)
Each water-stop film was evaluated for flexibility based on a 100% modulus evaluation method. Specifically, the reactive hot-melt adhesives of each test example were melted by heating at 120℃and a film having a thickness of 100 μm was formed on a release paper using a blade coater heated to 120℃and cured at 23℃and 50% RH for 72 hours, and then the 100% modulus was measured according to JIS K-7311-1995 and evaluated based on the following criteria. The results are shown in Table 1.
100% modulus of o = film less than 4MPa
The 100% modulus of the delta=film is 4MPa or more and less than 6MPa
X=100% modulus of film is 6MPa or more
TABLE 1
The waterproof slide fastener having a single-layer structure as the waterproof films of examples 1 to 4 was not evaluated in x in any of hydrolysis resistance, opening/closing durability, appearance, heat resistance, and flexibility. In particular, in example 1 in which a polycarbonate-polyether-polyester polyurethane urea is used as the water-blocking film, various characteristics can be exhibited with good balance. In addition, example 2, in which a polycarbonate-based polyurethaneurea was used as the water-blocking film, was particularly excellent in hydrolysis resistance. From the results, it is understood that when the water-blocking film is a laminated structure, various water-blocking films having excellent properties can be obtained when the surface layer is made of polycarbonate-based polyurethaneurea and the adhesive layer is made of polycarbonate-polyether-polyester-based polyurethaneurea.
On the other hand, in comparative example 1, since the polycarbonate component was not contained, the hydrolysis resistance and the heat resistance were insufficient. In comparative example 2, although a polycarbonate-polyether-polyester-based polyurethaneurea was used as the water-blocking film, the molar fraction of urea groups was too large, and the foaming amount was excessive, and the appearance was impaired. In comparative example 3, although a polycarbonate-polyether-polyester-based polyurethaneurea was used as the water-blocking film, the molar fraction of the urea groups was too small, and therefore abrasion was easy and the opening/closing durability was insufficient.
Claims (5)
1. A waterproof slide fastener comprising a pair of left and right fastener stringers, each of which comprises a fastener tape (10 a, 30) and a fastener row (21) attached to a side edge of the fastener tape (10 a, 30), wherein the fastener tape (10 a, 30) comprises a base fabric (11, 32) and a water-blocking film (12 a, 33) adhered to at least one side surface of the base fabric (11, 32), and the water-blocking film (12 a, 33) has a laminated structure comprising a surface layer (13) and an adhesive layer (14) of a cured body of a reactive hot-melt adhesive adjacent to the surface layer (13), wherein the adhesive layer (14) is directly adhered to the base fabric (11, 32) and the surface layer (13) between the base fabric (11, 32) and the surface layer (13), respectively.
2. The waterproof slide fastener according to claim 1, wherein the reactive hot-melt adhesive is a polycarbonate-based polyurethaneurea.
3. A method of manufacturing a waterproof slide fastener (20), comprising:
a step of manufacturing a pair of fastener tapes (10 a, 30) by performing a method for manufacturing the fastener tapes (10 a, 30);
a step of manufacturing a fastener stringer (27) by attaching a fastener element row (21) to a side edge of each of the fastener tapes (10 a, 30) manufactured; and
a step of attaching sliders (22, 29) between the left and right element rows (21) of the pair of fastener stringers (27),
the method for manufacturing the fastener tapes (10 a, 30) comprises:
a step of directly bonding the surface layer (13) to the base fabric (11, 32) by means of a reactive hot-melt adhesive; and
and a step of moisture-curing the reactive hot-melt adhesive.
4. A method of manufacturing a waterproof slide fastener (20), comprising:
a step of manufacturing a pair of fastener tapes (10 a, 30) by performing a method for manufacturing the fastener tapes (10 a, 30);
a step of manufacturing a fastener stringer (27) by attaching a fastener element row (21) to a side edge of each of the fastener tapes (10 a, 30) manufactured; and
a step of attaching sliders (22, 29) between the left and right element rows (21) of the pair of fastener stringers (27),
the method for manufacturing the fastener tapes (10 a, 30) comprises:
a step of sequentially laminating or simultaneously laminating a reactive hot-melt adhesive for the adhesive layer (14) and a reactive hot-melt adhesive for the surface layer (13) on the base fabrics (11, 32); and
a step of moisture-curing the reactive hot-melt adhesive for the adhesive layer (14) and the reactive hot-melt adhesive for the surface layer (13) together,
wherein the adhesive layer (14) is directly adhered to the base cloth (11, 32) and the surface layer (13), respectively.
5. The method for manufacturing a waterproof slide fastener (20) according to claim 3 or 4, wherein the reactive hot-melt adhesive is a polycarbonate-based polyurethaneurea.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110800451.3A CN113498915B (en) | 2016-07-01 | 2016-07-01 | Waterproof slide fastener and method for manufacturing waterproof slide fastener |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110800451.3A CN113498915B (en) | 2016-07-01 | 2016-07-01 | Waterproof slide fastener and method for manufacturing waterproof slide fastener |
| CN201680086207.2A CN109195475B (en) | 2016-07-01 | 2016-07-01 | Fastener tape, slide fastener provided with same, and method for manufacturing fastener tape |
| PCT/JP2016/069668 WO2018003119A1 (en) | 2016-07-01 | 2016-07-01 | Fastener tape, slide fastener provided with fastener tape, and method for manufacturing fastener tape |
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| CN201680086207.2A Division CN109195475B (en) | 2016-07-01 | 2016-07-01 | Fastener tape, slide fastener provided with same, and method for manufacturing fastener tape |
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| CN113498915A CN113498915A (en) | 2021-10-15 |
| CN113498915B true CN113498915B (en) | 2023-09-26 |
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| CN202110800451.3A Active CN113498915B (en) | 2016-07-01 | 2016-07-01 | Waterproof slide fastener and method for manufacturing waterproof slide fastener |
| CN201680086207.2A Active CN109195475B (en) | 2016-07-01 | 2016-07-01 | Fastener tape, slide fastener provided with same, and method for manufacturing fastener tape |
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| CN (2) | CN113498915B (en) |
| TW (1) | TWI620527B (en) |
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| CN111374399A (en) * | 2018-12-26 | 2020-07-07 | Ykk株式会社 | Fastener stringer and method for manufacturing fastener stringer |
| WO2021048936A1 (en) * | 2019-09-11 | 2021-03-18 | Ykk株式会社 | Zipper chain and method for producing zipper chain |
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|---|---|---|---|---|
| CN1272346A (en) * | 1999-04-30 | 2000-11-08 | Ykk株式会社 | Water-proof zipper and its making method |
| CN103260453A (en) * | 2010-12-17 | 2013-08-21 | Ykk株式会社 | Fastener stringer and fastener chain, and method for manufacturing fastener chain |
| TW201429718A (en) * | 2013-01-18 | 2014-08-01 | Formosan Rubber Group Inc | Wash-resistant, waterproof, permeable and durable leather material and production method thereof |
| CN104470398A (en) * | 2012-07-09 | 2015-03-25 | Ykk株式会社 | Fastener tape, slide fastener provided with same, and fastener tape fabrication method |
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| EP1084030A4 (en) * | 1998-04-07 | 2002-05-29 | Seydel Res Inc | Water dispersible/redispersible hydrophobic polyester resins and their application in coatings |
| US6105214A (en) * | 1998-09-25 | 2000-08-22 | Press; Stuart | Water resistant slide fastener and process for preparing same |
| JP4038608B2 (en) * | 2002-02-25 | 2008-01-30 | 大日本インキ化学工業株式会社 | Solvent-free, moisture-curable hot-melt urethane resin composition excellent in durability, foam, and sheet structure using the same |
| JP4344673B2 (en) * | 2003-10-15 | 2009-10-14 | フタムラ化学株式会社 | Gas barrier film |
| EP1674529A4 (en) * | 2003-10-15 | 2007-09-12 | Mitsui Takeda Chemicals Inc | Water-based resin composition with gas-barrier property and layered film made with the same |
| WO2008065921A1 (en) * | 2006-12-01 | 2008-06-05 | Dic Corporation | Moisture-curable polyurethane hot melt adhesive and multilayer sheet using the same |
| JP5360516B1 (en) * | 2012-04-12 | 2013-12-04 | Ｄｉｃ株式会社 | Moisture curable polyurethane hot melt resin composition, adhesive and article |
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2016
- 2016-07-01 CN CN202110800451.3A patent/CN113498915B/en active Active
- 2016-07-01 WO PCT/JP2016/069668 patent/WO2018003119A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272346A (en) * | 1999-04-30 | 2000-11-08 | Ykk株式会社 | Water-proof zipper and its making method |
| CN103260453A (en) * | 2010-12-17 | 2013-08-21 | Ykk株式会社 | Fastener stringer and fastener chain, and method for manufacturing fastener chain |
| CN104470398A (en) * | 2012-07-09 | 2015-03-25 | Ykk株式会社 | Fastener tape, slide fastener provided with same, and fastener tape fabrication method |
| TW201429718A (en) * | 2013-01-18 | 2014-08-01 | Formosan Rubber Group Inc | Wash-resistant, waterproof, permeable and durable leather material and production method thereof |
Also Published As
| Publication number | Publication date |
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| CN109195475A (en) | 2019-01-11 |
| TWI620527B (en) | 2018-04-11 |
| TW201801634A (en) | 2018-01-16 |
| CN109195475B (en) | 2021-08-03 |
| CN113498915A (en) | 2021-10-15 |
| WO2018003119A1 (en) | 2018-01-04 |
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