JP4517277B2 - Slide fastener parts and slide fasteners suitable for dyeing - Google Patents

Description

  The present invention relates to a slide fastener, and more particularly to a dyed slide fastener attached to clothing, a bag, or the like. The present invention relates to a fastener that can be dyed in the same bath because the color difference between the resin component consisting of a tooth, element, slider, and stopper and the fabric is very small even when dyed in the same bath with the fabric.

In general, a slide fastener is called a service tooth (also referred to as an element or teeth) 1, a fastener tape 2, a slider (opening / closing parts: a slider body 3 and a handle 4), and a stop as shown in FIG. It comprises a bottom stop 5 (sometimes referred to as a bottom stop) and, if necessary, a top stop (sometimes referred to as a top stop, not shown). Are engaged and the tape is closed, or the element is detached and the tape is opened.
Conventionally, as the element and slider, a high-strength metal, polyoxymethylene having good formability and wear resistance, and the like are used. However, since elements and sliders made of metal or polyoxymethylene have low dyeability and cannot be dyed in the same manner as the cloth or the tape, they have been pre-colored by painting or pigment. Further, the element and slider made of polyoxymethylene have a problem of melting when the iron touches during ironing.

Fasteners using dyeable polyester resins as elements and sliders are also disclosed (Japanese Patent Laid-Open Nos. 7-23811, 10-243805, and 2002-253306). However, in this case as well, the dyeability is greatly different from the fabric or the tape, and the color tone does not match, so it must be colored with a pigment before molding or dyed separately from the fabric after molding, and it is made of a dyeable resin. Slide fasteners were not universal. Further, an element and a slider made of non-reinforced polybutylene terephthalate resin have a problem that the bending elastic modulus is as low as about 2.3 GPa and is deformed at the time of opening and closing. Also, in the element and slider made of reinforced polybutylene terephthalate, especially when the content of the fibrous reinforcing material is more than 20% by mass, warpage and deformation increase, and the switching resistance is large due to dimensional accuracy and partial chipping. And wear was large, and the application was limited to a very small part. As disclosed in Japanese Patent Application Laid-Open No. 2000-7924, attempts have been made to lower the open / close resistance by adding a slidability improver, but the improvement has not been sufficient. Although the use of polyethylene terephthalate was also attempted, it was difficult to mold with a complicated mold to mold with a normal composition, and productivity was impossible. In the case of a slide fastener part that requires high dimensional accuracy, there is a problem in opening and closing during use due to deformation of the product at the time of release.
JP-A-7-23811 JP-A-10-243805 JP 2002-253306 A JP 2000-7924 A

In addition, when slide fasteners made of polyethylene terephthalate resin or polyamide resin are dyed in the same bath with polyethylene terephthalate resin or polyamide resin fabric, the slide fastener becomes darker, and the color tone of the fabric and slide fastener is different. Due to lack of merchantability, diversified production by bath dyeing could not be put into practical use industrially.
In the case of the same bath dyeing, the slide fastener is more concentrated even if fillers such as titanium oxide and zinc sulfide are blended to adjust the color of the slide fastener parts to the color of the fabric, and the crystallinity by heat treatment is adjusted. It became a color and the color tone did not match, so it could not be put to practical use.

  The present invention has been made against the background of the problems of the prior art, and when a slide fastener made of a fabric and a resin part is dyed in the same bath, the fabric and the slide fastener are dyed so that the appearance is the same color. And It is an object of the present invention to provide dyed fabrics and slide fasteners that are economically diverse and have high merchandise by providing slide fasteners having a small color difference from the fabric even when bath dyed.

As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention, (A) component and (B), (C), (D) and a resin composition comprising at least one component selected from the group consisting of (E), and the surface ten A slide fastener component characterized by being a satin surface having a point average roughness of 7 to 200 μm .
(A) Polyolefin polymer having a glass transition point of 0 ° C. or less and polyester dispersed as a domain having an average dispersed particle size of 0.1 to 2 μm in a matrix comprising a polyester resin and / or a polyamide resin (B) (A) Polymer or acrylic polymer (C) At least one inorganic compound selected from the group consisting of titanium compounds, zinc compounds and silicon compounds (D) From the group consisting of glass fibers, acicular wollastonite and aramid fibers At least one release agent selected from the group consisting of at least one fibrous reinforcing material (E) silicon compound, higher fatty acid ester compound, and higher fatty acid salt compound

  The slide fastener made of slide fastener parts according to the present invention can be dyed together with fabric and resin slide fastener parts, so non-dyed products can be mass-produced and the colors can be diversified by the same bath dyeing in the final process. It is. Since the slide fasteners can be dyed after being sewn on the fabric, they can be dyed appropriately as compared with the case where they are dyed before sewing, so that they are useful as commercial products. Productivity is high without producing many coloring materials, loss of color change, and inventory. In the case of the present invention, since the material of the fabric and the slide fastener is basically the same material, there is an advantage that the material can be recycled without being separated after being used.

Hereinafter, the present invention will be described in detail.
The resin composition containing the polyester resin and / or polyamide resin used in the present invention is selected from the group consisting of the following components (A) and (B), (C), (D) and (E). At least one component.
(A) polyester resin and / or polyamide resin,
(B) a polymer having a glass transition point of 0 ° C. or less dispersed as a domain having an average dispersed particle diameter of 0.01 to 3 μm in the matrix comprising (A),
(C) at least one inorganic compound selected from the group consisting of titanium compounds, zinc compounds and silicon compounds,
(D) a fibrous reinforcement,
(E) At least one mold release agent selected from the group consisting of silicon compounds, higher fatty acid ester compounds, and higher fatty acid salt compounds.

  The polyester resin used in the present invention is a polyester resin having 80% by mole or more of alkylene terephthalate repeating units. Examples of the glycol component include ethylene glycol, 1,3 propylene glycol, butanediol, neopentyl glycol, cyclohexanedimethanol, diethylene glycol, polyethylene glycol, polytetramethylene glycol, and the like. As the acid component, isophthalic acid, adipic acid, succinic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid and the like may be copolymerized in addition to terephthalic acid. Oxyacids such as polylactone may be copolymerized. Specific examples include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and copolymers thereof. Among them, polyethylene terephthalate and this copolymer are preferable because they have high strength and rigidity, are similar in physical properties to fabric materials, and are easy to handle. When the alkylene terephthalate repeating unit is less than 80 mol%, the crystallinity is lowered, and the moldability and rigidity are lowered.

  Moreover, it is also possible to use recycled products (also called recovered products, for example, recycled pellets) such as bottles, films, and fibers as the polyester resin. The use of recycled products is also preferable from the viewpoint of social demands for promoting a recycling-oriented society. For example, clothes made of polyester fibers and polyester slide fasteners can be re-pelletized to produce recycled pellets, and the polyester slide fasteners of the present invention can be manufactured using the recycled pellets as raw materials. The flakes obtained by pulverizing the regenerated product and those obtained by melting and pelletizing the flakes with an extruder can be used, but the shape is not limited.

  Examples of the polyamide resin used in the present invention include polyamide 6, polyamide 66, polyamide MXD6, polyamide 6T, polyamide 11 and polyamide 12. In addition, a polyamide resin obtained by copolymerizing dicarboxylic acid or diamine with 20 mol% or less may be used. Particularly preferred are polyamide resins having at least 80 mol% of capramide repeating units and / or polyamide resins having at least 80 mol% of hexamethylene adipamide repeating units. As the dicarboxylic copolymer component, adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid and the like are used. Examples of the diamine copolymer component include hexamethylene diamine, heptamethylene diamine, diaminobutane, and metaxylylene diamine.

As the polymer having a glass transition point of 0 ° C. or less dispersed as a domain having an average dispersed particle size of 0.01 to 3 μm in the matrix comprising the component (A) (B), a polyolefin polymer and an acrylic polymer , Polyester polymers, butadiene polymers, urethane polymers, and the like. Among these, polyolefin polymers, polyester polymers, and acrylic polymers are particularly preferable.
Examples of the polyolefin polymer include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-α olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer. Examples thereof include polymers, and these acrylic acid-modified products, these maleic anhydride-modified products, and these epoxy-modified products. Among these, an acrylic acid copolymer, a maleic anhydride modified product, and an epoxy modified product are preferable, and a maleic anhydride modified product of polyolefin and an epoxy modified product of polyolefin are particularly preferable, and a maleic anhydride modified product of polyolefin is more preferable. And an epoxy modified product of polyolefin are preferred.
As the polyester polymer, for example, a polyether polyester block copolymer, a polyester polyester block copolymer, or the like is used. Specific examples include a polytetramethylene glycol polybutylene terephthalate copolymer, a polypropylene glycol polybutylene terephthalate copolymer, a polyethylene glycol polybutylene terephthalate copolymer, and a polylactone polybutylene terephthalate copolymer.
As the acrylic polymer, for example, an alkyl acrylate alkyl methacrylate block polymer, an alkyl acrylate alkyl methacrylate styrene copolymer, or the like is used. As this alkyl group, methyl, ethyl, butyl and the like are preferable. Further, those in which a carboxyl group, an epoxy group, a silanol group, or a siloxane group is introduced are preferable in that the dispersed particle size can be easily adjusted. Moreover, these powder rubbers made into the core-shell type are preferable in terms of good control of the dispersed particle size and good handleability because the particle size can be adjusted.

In the present invention, the dispersed particle diameter of the polymer (B) is 0.01 to 3 μm, preferably 0.1 to 2 μm. This is related to an increase in scattered light of light incident on the slide fastener. When the dispersed particle diameter of the polymer (B) is less than 0.01 or more than 3 μm, it is not preferable because it is dyed in a deeper color than the fabric when dyed in the same bath together with the fabric.
Moreover, the compounding quantity of a polymer (B) is 1-30 mass parts with respect to 100 mass parts of polyester resins, Preferably it is 2-25 mass parts, Especially 3-23 mass parts is desirable. If the amount is less than 1 part by mass, the amount of scattered light is insufficient, and if it exceeds 30 parts by mass, the color becomes light and the wear resistance also decreases.

  In the present invention, as the at least one inorganic compound (C) selected from the group consisting of a titanium compound, a zinc compound and a silicon compound, specifically, titanium oxide, zinc oxide, zinc sulfide, talc, clay , Silica, wollastonite, mica, bentonite and the like. In particular, it is preferable to use titanium oxide, zinc oxide, or zinc sulfide, which has a high effect of concealing the coloring by the dye, because the appearance is dyed in the same color as clothing. In particular, a combination of titanium oxide and talc is preferable because an effect can be obtained by adding a small amount. Moreover, the compounding quantity of an inorganic compound (C) is 0.1-10 mass parts with respect to 100 mass parts of polyester resins, Preferably it is 0.1-7 mass parts, Especially 0.2-5 mass parts is desirable. If it is less than 0.1 parts by mass, it is not preferable because it becomes dark when dyed in the same manner as the fabric, and if it exceeds 10 parts by mass, the color tone is not deep and wear resistance is lowered, which is not preferable as a slide fastener. Moreover, as a shape of an inorganic compound (C), granular powder, plate-shaped powder, etc. are preferable.

Examples of the fibrous reinforcing material (D) used in the present invention include glass fibers, carbon fibers, acicular wollastonite, inorganic fibers such as whiskers such as calcium titanate and aluminum borate, aramid fibers and polyphenylene sulfide fibers. A heat-resistant organic fiber is mentioned. In particular, glass fiber, acicular wollastonite, and aramid fiber are preferable. The fiber diameter is preferably 1 to 30 μm, particularly preferably 10 to 20 μm. The fiber length in the molded product is preferably 0.05 mm to 0.5 mm, more preferably 0.1 mm to 0.4 mm.
The fibrous reinforcing material (D) is blended in an amount of 0.1 to 200 parts by weight, preferably 0.5 to 150 parts by weight, and particularly preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polyester resin (A). If the amount is less than 0.1 parts by mass, the effect of improving the strength and rigidity is small, and if it exceeds 200 parts by mass, the bond between the fibrous reinforcing materials (D) becomes weak, so that it becomes brittle and the strength decreases.

  Said inorganic compound (C) and fibrous reinforcement (D) may be processed by the silane coupling agent, the titanate coupling agent, etc. This treatment improves the strength and impact resistance of the molded product. In particular, those treated with an epoxy-based, acrylic-based, urethane-based, or amine-based coupling agent for improving the adhesion to the polyester resin are preferable.

  Examples of the release agent (E) used in the present invention include at least one selected from the group consisting of a silicon compound, a higher fatty acid ester compound, and a higher fatty acid salt compound. By blending the mold release agent (E), deformation at the time of mold release is prevented, the dimensional accuracy is improved, and the element and the slider are well meshed so that smooth opening and closing is possible. In particular, these release agents have moderate incompatibility with polyalkylene terephthalate, have a high release effect, and have high heat resistance. Furthermore, since the occurrence of bleeding, mottled patterns, uneven dyeing, etc. is suppressed in the molded product after dyeing, the appearance is good and the merchantability is not impaired.

  Specific examples of the release agent (E) include dimethylsiloxane compounds, methylphenylsilicon compounds, one-end or both-end reactive silicone oil modified with alcohol, epoxy, or acid, stearates, stearates. Examples include sodium, calcium stearate, magnesium stearate, zinc stearate, calcium montanate, montanate, sodium montanate, and montanate partial salt. Among them, dimethylsiloxane compounds, alcohol-modified silicone oil, montanate, Calcium montanate and montanate ester partial salts are preferred. These release agents are blended in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyester resin. If it is less than 0.1 parts by mass, the effect of preventing deformation at the time of mold release is small, and if it exceeds 10 parts by mass, bleeding, mottled patterns, and uneven dyeing occur on the surface of the molded product.

  In the present invention, in addition to the above (A) to (E), conventional additives such as a heat stabilizer, an anti-mold agent, a hydrolysis-resistant agent, and a pigment may be added. Examples of the heat stabilizer include hindered phenol compounds, thioether compounds, phosphite compounds, and combinations thereof. Examples of the antifungal agent include carbon black, benzophenone compounds, triazole compounds, hindered amine compounds, and the like. Examples of the hydrolysis resistance agent include carbodiimide, bisoxazoline, epoxy, and isocyanate compounds. Moreover, as a pigment, the heat-resistant pigment normally used for a polyalkylene terephthalate type polymer can be used.

The satin surface in the present invention is a surface having fine irregularities on the surface of the molded product, and has a surface on which light is irregularly reflected on the surface of the molded product. Preferably, it is a surface in which small irregularities are combined on large irregularities. The degree of the surface unevenness depends on the surface property and thickness of the fabric fiber, but the 10-point average roughness of the surface of the slide fastener part is selected in the range of 0.8 to 200 μm. If the surface is smooth and thick, it must be rough, and if it is irregular or thin, it must be fine.
The effect of pear texture is evaluated by the difference in glossiness and brightness between the mirror surface and pear ground. The brightness of the surface of the molded article dyed with the same bath increases depending on the degree of satin. In general, a satin finish having a lightness difference with the fabric of 10 or less, preferably 8 or less is used. In order to reduce the difference in lightness, the 10-point average roughness of the surface is preferably from 7 to 200 μm, and in particular, from 10 to 150 μm on the surface of a molded article.

  The matte finish on the surface of the molded article is preferably a mold having a satin finish on the molding surface, but can also be performed by post-processing such as sanding or pressing of the molded article. It is preferable that fine irregularities on the surface are strong, and etching by chemical treatment is preferable.

  As the dye in the present invention, various dyes can be used, but a disperse dye is preferable. Examples of the disperse dye include quinone disperse dyes, azo disperse dyes, and anthraquinone disperse dyes. For polyamide resins, acid dyes are also used. The acidic dye is dyed in an acidic bath with a dye having an acidic group in the molecule. Dyes having basic groups in addition to acidic groups such as sulfonic acid groups, carboxylic acid groups, and phenolic hydroxyl groups are preferred. Dyeing assistants such as leveling agents can be added to the dispersion bath. The slide fastener with tape is immersed in a dyeing solution having a dye concentration of 0.5 to 10%, preferably 1 to 4%, and is 100 to 150 ° C, preferably 110 to 140 ° C for 5 to 120 minutes, preferably 15 Processed for ~ 60 minutes. After washing with water, it was air-dried and dyed.

  As shown in FIG. 1, the slide fastener component of the present invention includes a tooth 1 (sometimes referred to as “element” or “teeth”) 1, a slider (including an opening / closing component: a slider body 3 and a handle 4), and a bottom called “stop”. It can be used for any one of a stop 5 (sometimes referred to as a bottom stop) and, if necessary, a top stop (sometimes referred to as a top stop, not shown). In particular, the effect of the present invention is significant in an element that needs to match the color tone with the tape. Preferably, all of these parts are slide fasteners comprising the parts of the present invention.

The slide fastener part of the present invention is manufactured by manufacturing the slide fastener resin composition and molding the composition. The resin composition can be produced by kneading each of the above-described constituents using an apparatus such as a single screw extruder, a twin screw extruder, or a kneader. There is no restriction | limiting in particular about the kind of kneading machine to be used, and kneading | mixing conditions. The slide fastener component of the present invention is a mold whose surface is roughened, for example, so that the ten-point average roughness of the surface of the molded product is in the range of 0.8 to 200 μm. It is manufactured by injection molding. The surface of the mold is roughened by sand digging or chemical etching in order to obtain a molded product having a matte surface. In some cases, the surface properties are adjusted thereafter by beading. Transferability from the mold surface to the surface of the molded product depends on the fluidity and solidification property of the resin. This difference is processed in advance so that the unevenness on the surface of the prospective mold becomes larger.
The molding method is not particularly limited, but is generally injection molding. In the case of a polyester resin, the mold temperature is preferably in the range of 30 to 60 ° C or 120 to 150 ° C. In the case of a polyamide resin, the mold temperature is preferably in the range of 30 to 80 ° C.

The shape of the slide fastener of the present invention is not particularly limited, and includes various slide fasteners. For example, the element is a monofilament coil fastener, a resin injection fastener, or the like. Moreover, the components for slide fasteners of this invention are components which can be used for various slide fasteners.
Further, when the textile product using the slide fastener of the present invention is recycled, it can be melt-molded without separating the fabric and the slide fastener.
Further, since the fiber and the slide fastener are the same material, the dispersibility is good and the physical property does not become a defect point. Therefore, material recycling is possible, and the recycled material can be used again in the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these Examples. The physical properties in the examples were measured by the following methods.

1. Ten-point average roughness of the surface of the molded product corresponding to the mold and the slide fastener parts The surface roughness meter of the differential inductance method (Surfcom 554A, manufactured by Tokyo Seimitsu Co., Ltd.) is used for the unevenness of the mold and the molded product. Then, a reference length of 25 mm was measured with a measuring force of 4 mN or less and a driving speed of 0.5 mm / sec with a tip radius of 5 μm made of diamond and a conical stylus. Ten-point average roughness (μm) was determined from the roughness curve according to JIS B0601-1994.

2. Color and bath dyeability of molded products corresponding to parts for slide fasteners (lightness difference between molded products and fabric)
A tape for evaluation and a flat plate for evaluation having various surface roughnesses were immersed in 1000 ml of a dyeing solution having a concentration of 2% by mass of Sumikaron (R) dye Navy Blue SE-RPD (manufactured by Sumitomo Chemical Co., Ltd.) at 130 ° C. After 30 minutes of treatment, the fabric and molded product were obtained by washing with water and air drying.
Using a color difference meter (TC1500MC-88 type, manufactured by Tokyo Denshoku Co., Ltd.), the color tone (L ₂ value, a value, b value) of the surface of the molded article having various irregularities, and L _{1 of the} slide fastener fabric tape The value was measured and the bath dyeing property was evaluated by ΔL (lightness difference) according to the equation (1).
ΔL = L ₂ −L ₁ (1)

(Examples 1-6, Comparative Examples 1-5)
(1) Production of a molded product corresponding to a slide fastener part: A raw material consisting of 100 parts by mass of polyethylene terephthalate resin, 5 parts by mass of maleic anhydride-modified polyethylene, 3 parts by mass of zinc sulfide, and 0.5 parts by mass of montanic acid ester is reserved. It was dried, melt-kneaded at a cylinder temperature of 270 ° C. and a screw rotation speed of 50 rpm with a twin screw extruder (Ikekai Tekko Co., Ltd., PCM30), extruded into a strand shape in a water bath, cooled, and then a resin composition pellet was obtained. . This was dried at 140 ° C. for 3 hours, then supplied to the hopper of an injection molding machine (Toshiba Machine Co., Ltd., IS80) adjusted to a cylinder temperature of 270 ° C., and the surface temperature was adjusted to 40 ° C. for a length of 35 cm. 100 cavities on both sides of the surface were obtained using the mirror surface shown in Table 1 and various 30mm x 70mm x 3mm molds with a matte finish to obtain flat plates with various surface roughnesses at 130 ° C. An evaluation sample was obtained after heat treatment for 20 minutes.

(2) Fabrication: An evaluation tape was obtained by plain weaving of multifilaments consisting of 30 fibers having a thickness of 1 dtex obtained by melt spinning a polyethylene terephthalate resin and then spinning.
(3) Result: As described above, using a molding die having a different surface roughness, a molded article having a ten-point average surface roughness as shown in Table 1 was obtained. These molded products and cloth were put in a stainless steel cylindrical container and dyed in the same bath. The hue L value, a value, and b value were measured on the surface of the dyed molded product and the fabric tape, and the brightness difference ΔL between the molded product and the fabric is shown in Tables 1 and 2.

  As is clear from Examples 1 to 6 and Comparative Examples 1 to 5, it can be seen that the molded product having the 10-point average roughness of the surface of the present invention comes close to the fabric and the color tone when dyed together with the fabric. .

  The slide fastener made of the resin slide fastener part of the present invention is used as a slide fastener for clothing, bedding, and leisure goods, dyed under the same bath and conditions as fabrics and products.

It is a figure which shows the one aspect | mode of a slide fastener.

Explanation of symbols

1: Tooth (element)
2: Slide fastener fabric tape 3: Slider body (slider body)
4: Pull tab (tab)
5: Bottom stop (bottom stop)

Claims (1)

Component (A) and (B), the ten-point average roughness (C), (D) and a resin composition comprising at least one component selected from the group consisting of (E), and the surface A slide fastener component characterized by having a 7-200 μm matte surface.
(A) Polyolefin polymer having a glass transition point of 0 ° C. or less and polyester dispersed as a domain having an average dispersed particle size of 0.1 to 2 μm in a matrix comprising a polyester resin and / or a polyamide resin (B) (A) Polymer or acrylic polymer (C) At least one inorganic compound selected from the group consisting of titanium compounds, zinc compounds and silicon compounds (D) From the group consisting of glass fibers, acicular wollastonite and aramid fibers At least one release agent selected from the group consisting of at least one fibrous reinforcing material (E) silicon compound, higher fatty acid ester compound, and higher fatty acid salt compound

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