TWI616521B - Zipper chain and zipper - Google Patents

Abstract

In a zipper chain using a polyester resin material as a waterproof coating film, the softness and transparency of the waterproof coating film are improved. A zipper chain has the following structure: a row of zipper fastener elements installed along respective side edge portions of a pair of zipper chain cloths with a waterproof coating film formed on at least one main surface is formed by mutual engagement; It is formed from a polyester resin composition containing an aliphatic dicarboxylic acid residue having 10 or more carbon atoms, an alicyclic dicarboxylic acid residue having 10 or more carbon atoms, and 10 or more carbon atoms. An aromatic polyester resin having one or two or more residues in a group consisting of an aliphatic diol residue and an alicyclic diol residue having a carbon number of 10 or more.

Description

Zipper chain and zipper

The invention relates to a zipper. The invention particularly relates to a ring-shaped zipper with a waterproof function.

Zippers are popular as opening and closing parts for daily necessities such as clothing, bags, footwear, and miscellaneous goods, but they are also used in protective clothing such as space suits, chemical protective clothing, wetsuits, lifeboats, and life jackets, and transportation containers. container) with protective covers or tents. For this special purpose, the zipper is also required to be waterproof.

Generally speaking, a zipper mainly includes the following three parts: a pair of elongated zipper chain cloths; zipper fasteners, which are installed along one side edge of each chain cloth, and serve as the engaging parts of the fasteners; and slides It controls the opening and closing of the fastener by engaging and separating the fastener element. Conventionally, a zipper has been known in which a synthetic resin film having a waterproof property is attached to a zipper chain cloth in order to impart waterproofness, and the synthetic resin films of the left and right zipper chain cloths are closely adhered to each other when the mesh is engaged, thereby exerting water resistance.

For example, in Japanese Patent Publication No. 2002-525143 (Patent Document 1), it is described that a roll or a laminated roll is used to attach a polyurethane to one side of a fastener chain cloth in a zipper by a transfer lamination method. Water-resistant film such as an acid film. In this publication, it is described that the film preferably has a multilayer structure having an outer wear-resistant layer and an inner low-temperature molten material. It is described that: by providing an abrasion-resistant layer, the abrasion resistance is increased, and the friction coefficient is reduced, thereby facilitating the operation; or by embedding a part of the low-temperature molten layer in the material of the zipper chain cloth , And improve the bonding strength between the film and the zipper chain cloth. It is also recorded that by including polyurethane The inner layer of the ester adhesive, bonding agent or hot-melt adhesive is coated with a polyurethane film.

In the Republic of China Patent No. I220106 (Patent Document 2), a method is described in which self-coated PU (Polyurethane, polyurethane) gel is applied to a zipper chain cloth by a roller device. The PU sheet of the release paper is pressurized to bond the PU gel with the PU sheet. Thereafter, the PU sheet and the PU gel are thermoplastically bonded by heating to form a waterproof layer.

Japanese Patent No. 4312171 (Patent Document 3) describes a method in which a liquid polyester synthetic resin-based waterproof material substance is penetrated into a zipper chain fabric to form a waterproof film.

In Japanese Patent Publication No. 1-14168 (Patent Document 4), it is described that as a waterproof sealing material layer, a synthetic rubber such as silicone rubber, butyl rubber, neoprene rubber, and polyurethane rubber is coated. Apply to the zipper chain cloth and allow it to dry.

In Japanese Patent No. 3580725 (Patent Document 5), it is described that a laminated synthetic resin film including a low-melting resin layer and a high-melting resin layer is heated in a state in which the low-melting resin layer and the surface of the fastener chain are in opposite contact Press on at least one side of the zipper chain cloth in the zipper to perform welding. As a material of the laminated synthetic resin film, a urethane resin and a polyester resin are disclosed.

Japanese Patent No. 5387812 (Patent Document 6) describes a method of extrusion-molding a coating layer including polyurethane, polypropylene, polyvinyl chloride, and a rubber thermoplastic material on a zipper chain The surface of the cloth. Specifically, the method includes the steps of: conveying a zipper chain cloth to an extrusion molding die; and extruding a coating layer of a waterproof polymer on the surface of the zipper chain cloth to form a waterproof layer.

In Japanese Patent Application Laid-Open No. 2012-24573 (Patent Document 7), it is described that a fin-shaped polymer material obtained by bulging a sprocket side is applied to the surface of a fastener chain cloth. It is also described that a coating of a polymer material is extruded and formed on a chain cloth. Examples of the polymer material include thermoplastic elasticity such as polychloroprene, polyurethane elastomer, and polyester elastomer. body. According to this document, a pair of fin-shaped polymer materials are closed to each other when the zipper is closed, thereby achieving a liquid-tight state on a joint surface of the polymer materials.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Publication No. 2002-525143

Patent Document 2: Republic of China Patent No. I220106

Patent Document 3: Japanese Patent No. 4312171

Patent Document 4: Japanese Patent Fairness No. 1-14168

Patent Document 5: Japanese Patent No. 3580725

Patent Document 6: Japanese Patent No. 5387812

Patent Document 7: Japanese Patent Laid-Open No. 2012-24573

In recent years, the awareness of environmental protection has increased, and due to this, it is required to produce products with a small environmental load. However, in the previous waterproof zipper, it was not realized that the type of resin used in the waterproof film and zipper chain cloth was set to The same, therefore, as the material of the waterproof film, synthetic rubber such as polyurethane is the mainstream, and the zipper chain cloth is generally made of polyester. However, if different types of resin are used for the waterproof film and the fastener chain cloth, there is a problem that the recyclability becomes difficult.

In addition, in order to ensure the bonding strength, in many cases, a film is coated with an adhesive and then affixed to a zipper chain fabric, which has a problem that the number of steps increases and the manufacturing cost increases. Since the adhesive also contains components harmful to the human body, there is also the problem that special training and special exhaust devices are required during manufacture.

Japanese Patent No. 4312171 (Patent Document 3) describes a method for forming a waterproof film by infiltrating a liquid polyester synthetic resin-based waterproof material into a zipper chain cloth structure. Japanese Patent Laid-Open No. 2012-24573 In Japanese Patent Publication (Patent Document 7), a polyester elastomer is also cited as a polymer material for coating the surface of a fastener chain. However, if you use When a polyester resin-based material forms a waterproof film, there is a problem that the appearance of the waterproof film is impaired due to poor transparency. In addition, since a waterproof film formed of a polyester-based resin material has low flexibility, problems such as deterioration of the sliding property of a slider and deterioration of the texture of a zipper chain cloth also occur.

The present invention was made by the creator in view of the above-mentioned circumstances, and one of its problems is to improve the flexibility and transparency of the waterproof coating film in a zipper chain using a polyester resin material as a waterproof coating film. Another object of the present invention is to provide a slide fastener including such a slide fastener chain.

In one aspect, the present invention is a zipper chain, which has the following structure: the rows of zipper fastener elements mounted on the respective side edge portions of a pair of zipper chain cloths having a waterproof coating film formed on at least one main surface are engaged with each other and And the waterproof coating film is formed of a polyester resin composition containing an aliphatic dicarboxylic acid residue having a carbon number of 10 or more and an alicyclic dicarboxylic acid having a carbon number of 10 or more An aromatic polyester resin having one or two or more residues in a group consisting of a residue, an aliphatic diol residue having 10 or more carbon atoms, and an alicyclic diol residue having 10 or more carbon atoms.

In one embodiment of the fastener chain of the present invention, the above-mentioned aliphatic dicarboxylic acid residue having a carbon number of 10 or more in the total of the total acid component residues and the total diol component residues in the aromatic polyester resin, The total content ratio of the alicyclic dicarboxylic acid residue having 10 or more carbon atoms, the aliphatic diol residue having 10 or more carbon atoms, and the alicyclic diol residue having 10 or more carbon atoms is 0.5 to 8 moles. ear%.

In still another embodiment of the zipper chain of the present invention, the aromatic polyester resin has one of the aliphatic dicarboxylic acid residues having the carbon number of 10 or more and the aliphatic dicarboxylic acid residues having the carbon number of 10 or more. At least one serves as a dimer acid residue.

In still another embodiment of the zipper chain of the present invention, the aromatic polyester resin has at least one of the aliphatic diol residue having the carbon number of 10 or more and the alicyclic diol residue having the carbon number of 10 or more. As a dimer diol residue.

In still another embodiment of the zipper chain of the present invention, the dimer acid residue is a hydrogenated dimer acid residue.

In still another embodiment of the zipper chain of the present invention, the dimer diol residue is a hydrogenated dimer diol residue.

In another embodiment of the fastener chain of this invention, the said polyester resin composition contains a polycarbodiimide.

In another embodiment of the fastener chain of this invention, the said polyester resin composition contains a lubricant.

In another embodiment of the fastener chain of this invention, the said polyester resin composition contains at least one of a ultraviolet absorber and a pigment.

In another embodiment of the fastener chain of this invention, the content ratio of the said aromatic polyester resin in the said polyester resin composition is 60 mass% or more.

In still another embodiment of the zipper chain of the present invention, the zipper chain cloth is made of polyester resin.

In still another embodiment of the zipper chain of the present invention, the above-mentioned waterproof coating film enters the unevenness of the main surface of the zipper chain cloth at the interface with the zipper chain cloth.

In another embodiment of the fastener chain of this invention, the said waterproof coating film is dyed.

The present invention is, in another aspect, a zipper provided with the zipper chain of the present invention.

The present invention is, in yet another aspect, an article provided with the zipper of the present invention.

According to the zipper chain of the present invention, the following effects can be obtained.

(1) Since the waterproof coating film of the present invention has high transparency, the color of the cloth of the zipper chain cloth can also be maintained after the waterproof coating film is formed. Therefore, it is possible to achieve both waterproofness and aesthetics. In addition, when the waterproof coating film is dyed, it can be easily adjusted to a desired hue.

(2) Since the waterproof coating film of the present invention is excellent in flexibility, it is possible to suppress the deterioration of the texture of the zipper chain cloth or the deterioration of the sliding property of the slider caused by the formation of the waterproof coating film.

(3) When the zipper chain cloth is made of polyester resin-based material, the zipper chain cloth and the waterproof coating film become the same kind of resin, so it can be made into a zipper chain with high recyclability and environmental friendliness.

(4) The waterproof coating film of the present invention can also be directly formed on a zipper chain cloth without using an adhesive. Therefore, it is conducive to improving the working environment and does not require special facilities or training. Moreover, compared with the method of sticking a waterproof film by an adhesive agent, the number of steps can be reduced, and manufacturing cost can also be suppressed.

10‧‧‧ Zipper

11‧‧‧ sprocket

12‧‧‧ Slide

13‧‧‧ core rope

14‧‧‧ suture

15‧‧‧ pull

16‧‧‧ Upper stop

18‧‧‧Zipper chain cloth

19‧‧‧Waterproof coating

21‧‧‧Zipper chain

22‧‧‧ polyester resin composition

23‧‧‧Mould

24‧‧‧ Extruder

25‧‧‧ Resin composition coated surface side roller

26‧‧‧Resin composition non-coated side roller

30‧‧‧Fixed fixture

32‧‧‧Water storage member

34‧‧‧ opening member

36‧‧‧Test sample

38‧‧‧ Angle Fixture

40‧‧‧ spray nozzle

42‧‧‧Piping

44‧‧‧Water volume regulating valve

46‧‧‧ Sekisui

48‧‧‧ overflow

50‧‧‧ softness tester

51‧‧‧moving components

52‧‧‧Loading Yuan

53‧‧‧Pressurizer

54‧‧‧ plywood

60‧‧‧Test sample

60a‧‧‧Ring

60b‧‧‧ overlap

A‧‧‧ mesh centerline

g‧‧‧distance

s‧‧‧ interval

w‧‧‧ slit width

FIG. 1 is a plan view of a slide fastener according to an embodiment of the present invention.

Fig. 2 is a sectional view of a slide fastener according to an embodiment of the present invention.

3 is a perspective sectional view of a slide fastener according to an embodiment of the present invention.

FIG. 4 shows an example of the structure of a device for forming a waterproof coating film on a zipper chain.

FIG. 5 shows a plan view and a side cross-sectional view of a fixing jig used for a test piece of the rain test B method (a view viewed in the direction of the arrow A-A).

FIG. 6 shows the appearance of an artificial rainfall device when the rain test method B is performed.

FIG. 7 shows a state where water accumulates in the water storage member by sprinkling water and permeates the test piece, and water accumulates.

FIG. 8 shows a state before the flexibility test device is operated.

FIG. 9 shows a state during operation of the flexibility test apparatus.

(1.Zipper chain)

Hereinafter, the embodiment of the zipper chain of the present invention will be described in detail with reference to the drawings. An example of the slide fastener 10 provided with the slide fastener chain of this invention is shown to FIGS. 1-3. FIG. 1 is a plan view of the whole of the zipper 10, and FIG. 2 is a diagram showing the rows of the fastener elements 11 on the slider 12 is a sectional view of the case of internal engagement, and FIG. 3 is a perspective sectional view of a part of the zipper 10.

A state in which a fastener element row is attached to each zipper chain cloth is called a zipper chain belt. In addition, a pair of each fastener chain belt and a fastener element are called a fastener chain. A slide fastener, an upper stopper, and a lower stopper are attached to a zipper chain.

In one embodiment, the zipper chain of the present invention has a structure in which rows of zipper fastener elements mounted on respective side edge portions of a pair of zipper chain cloths having a waterproof coating film formed on at least one main surface are engaged with each other. . Referring to FIGS. 2 and 3, a row of sprocket teeth 11 is mounted on one main surface of each fastener chain cloth 18 along one edge thereof. A slider 12 is inserted between the rows of left and right fastener element 11, and the sliding state of the slider 10 can be controlled by sliding the slider 12. Further, the upper stopper 16 may be provided as shown in FIG. 1. Although not shown, a lower stopper, a detachable insert, etc. may be installed. The pair of zipper chain cloths 18 preferably have one side edges adjacent to each other at a predetermined interval (s = 30 to 600 μm in FIG. 2). The space is provided between the two in order to make the sliding property of the slider 12 good. Although not limited, the fastener chain cloth 18 is generally a long rectangular shape.

In the embodiment shown in the figure, the rows of thread-like zipper fastener elements 11 of the thread type in which the core rope 13 is inserted inside are sewn separately by stitches 14. Here, a double chain stitch of a sewing machine is applied to the stitches 14. The rows of the ring-shaped fastener element 11 may be formed of monofilaments of synthetic resin such as polyamide and polyester, but from the viewpoint of improving recyclability, it is preferably made of polyester resin. There are no particular restrictions on the materials of the slider 12, the suture 14, and other components, but by using a polyester resin, the recyclability can be further improved.

(1-1. Waterproof coating)

In the illustrated embodiment, a waterproof coating film 19 made of a polyester resin composition is formed on the other main surface of each of the fastener chain cloths 18. In the present invention, one of the characteristics is that the waterproof coating film 19 is formed of a polyester resin composition containing an aliphatic dicarboxylic acid residue having a carbon number of 10 or more and a carbon number of 10 or more. The above-mentioned alicyclic dicarboxylic acid residues, aliphatic diol residues having a carbon number of 10 or more, and alicyclic diol residues having a carbon number of 10 or more An aromatic polyester resin having one or two or more residues in a group (hereinafter, these residues may be collectively referred to as "residues having 10 or more carbon atoms"). Thereby, it is possible to form a waterproof coating film in which the crystallinity of the polyester resin is reduced and the flexibility and transparency are excellent.

The so-called polyester resin repeatedly has a dicarboxylic acid (in the present invention, a "dicarboxylic acid" includes an ester derivative component thereof) and a diol component such as an aliphatic diol, an alicyclic diol, and an aromatic diol. Resin structured by esterification. One of the characteristics of the waterproof coating film of the present invention is that an aromatic polyester resin is particularly used in the polyester resin. By using an aromatic polyester resin, the advantage of being excellent in heat resistance can be obtained.

The aromatic polyester resin refers to a polyester resin using at least one of an aromatic dicarboxylic acid and an aromatic diol as a monomer. Therefore, the aromatic polyester resin has at least one of a plurality of aromatic dicarboxylic acid residues and aromatic diol residues. In a preferred embodiment, the aromatic polyester resin has a plurality of aromatic dicarboxylic acid residues. Therefore, in one embodiment of the aromatic polyester resin of the present invention, it has one or two or more of aromatic dicarboxylic acid residues and aromatic diol residues, and residues having 10 or more carbon atoms. One or more of them.

Examples of the dicarboxylic acid include aromatic dicarboxylic acid and aliphatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, and 1,5- Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Examples of aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, and pimelic acid. , Suberic acid, azelaic acid, sebacic acid, dodecanedioic acid. For reasons of excellent heat resistance, an aromatic dicarboxylic acid is preferred. Examples of the ester derivative component include alkyl esters and halogen halides of these acids. Examples of the aliphatic diol include ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and triethylene glycol. . Examples of the alicyclic diol include cyclohexanediol and 1,4-cyclohexanedimethanol. Examples of the aromatic diol include 4-bishydroxyethoxybenzene and bisphenol A. Further examples of the diol include polymer diols such as polyethylene glycol, polytetramethylene glycol, and polyhexamethylene glycol. Can also be These acid components and diol components are used in combination of a plurality of types.

One or two or more aromatic polyester resins having a residue of 10 or more carbon atoms can be selected from aliphatic dicarboxylic acids of 10 or more carbon atoms and alicyclic dicarboxylic acids of 10 or more carbon atoms. One or two or more compounds in the group consisting of aliphatic diols having a carbon number of 10 or more and alicyclic diols having a carbon number of 10 or more are used as monomers, and are used in combination with the aromatic polyester resins. It is manufactured by copolymerizing other monomers. In this case, the residue having a carbon number of 10 or more may be incorporated into the backbone of the polyester. If only selected from the group consisting of an aliphatic dicarboxylic acid having 10 or more carbon atoms, an alicyclic dicarboxylic acid having 10 or more carbon atoms, an aliphatic diol having 10 or more carbon atoms, and an alicyclic diol having 10 or more carbon atoms If one or two or more compounds in the composition group are mixed with the polyester resin, the desired effect cannot be obtained.

An aliphatic dicarboxylic acid having 10 or more carbon atoms, an alicyclic dicarboxylic acid having 10 or more carbon atoms, an aliphatic diol having 10 or more carbon atoms, and an alicyclic diol having 10 or more carbon atoms are excellent in transparency. For reasons, the number of carbons is preferably 20 or more, and more preferably 30 or more. About the aliphatic dicarboxylic acid with a carbon number of 10 or more, the alicyclic dicarboxylic acid with a carbon number of 10 or more, the aliphatic diol with a carbon number of 10 or more, and the alicyclic diol with a carbon number of 10 or more, the upper limit of the carbon number Although not specifically set, from the viewpoint of solvent resistance and heat resistance, it is preferably 54 or less, and more preferably 40 or less.

The aliphatic dicarboxylic acid having 10 or more carbon atoms, the alicyclic dicarboxylic acid having 10 or more carbon atoms, the aliphatic diol having 10 or more carbon atoms, and the alicyclic diol having 10 or more carbon atoms may be linear Either the shape or the branched shape may be either saturated or unsaturated, but it is preferably a branched shape because it is excellent in softness and transparency, and it is preferable because it is colorless and transparent. Saturated.

The aliphatic dicarboxylic acid having a carbon number of 10 or more is not limited, but examples thereof include sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. And branched aliphatic saturated dicarboxylic acids such as heptadecanedioic acid, cetaneedioic acid, octadecanedioic acid, and eicosenedioic acid; decanedioic acid, undecenedioic acid , Dodecenedioic acid, Tridecenoic acid, tetradecanedioic acid, heptadecenedioic acid, and hexadecenedioic acid, such as linear and branched aliphatic unsaturated dicarboxylic acids.

Although the alicyclic dicarboxylic acid having a carbon number of 10 or more is not limited, it may be exemplified by a cycloalkane or a cycloolefin having two -A-COOH (wherein A represents a carbon number of 1 or 2) The compound obtained by the above-mentioned divalent saturated or unsaturated chain hydrocarbon group so that the carbon number of the entire compound becomes 10 or more). Examples of the cycloalkane include cyclohexane, cyclopentane, and cycloheptane. Examples of the cycloolefin include cyclohexene, cyclopentene, and cycloheptene. As a more specific example, a base represented by-(CH ₂ ) _n -COOH (n is an integer of 1 or more) is bonded to the 1st and 4th positions, or the 1st and 3rd positions of cyclohexane, respectively. The compound obtained; at positions 1 and 3 of the cyclopentane ring, respectively,-(CH ₂ ) _n -COOH (n is an integer of 1 or more) and-(CH ₂ ) _m -COOH (m is 2 or more) Integer)).

Although the aliphatic diol having a carbon number of 10 or more is not limited, for example, decanediol, undecanediol, dodecanediol, tridecanediol, tetradecanediol, Pentadecanediol, cetanediol, heptadecanediol, octadecanediol, undecanediol, eicosanediol, behenanediol, behenanediol, Tsancosanediol, Tetracosanediol, Titanate, Titanate, Titanate, Titanate, Titanate, Titanate Linear and branched aliphatic saturated diols, such as dodecanediol, 31-decanediol, and dodecanediol; decenediol, dodecenediol, tetradecenediol, Linear and branched aliphatic unsaturated diols such as cetene diol and stearyl diol.

Although the alicyclic diol having a carbon number of 10 or more is not limited, it may be exemplified by a cycloalkane or a cycloolefin having two -B-OH (wherein, B represents a carbon number of 1 or 2 or more) A compound obtained by a functional group represented by a divalent saturated or unsaturated chain hydrocarbon group such that the carbon number of the entire compound becomes 10 or more). Examples of the cycloalkane include cyclohexane, cyclopentane, and cycloheptane. Examples of the cycloolefin include cyclohexene, cyclopentene, and cycloheptene. More specific examples include the following:-(CH ₂ ) _n -OH (where n is an integer of 2 or more) is bonded to the 1st and 4th positions, or the 1st and 3rd positions of the cyclohexane ring, respectively. Compound obtained from a radical; 1- and 3-positions of the cyclopentane ring are respectively bonded with-(CH ₂ ) _n -OH (n represents an integer of 2 or more) and-(CH ₂ ) _m -OH (m represents 3 The compound obtained by the above integer).

In a preferred embodiment of the present invention, the aromatic polyester resin has at least one of the aliphatic dicarboxylic acid residue having 10 or more carbon atoms and the alicyclic dicarboxylic acid residue having 10 or more carbon atoms. Dimer acid residue.

"Dimer acid" is a polycarboxylic acid obtained by polymerizing two or more molecules of an unsaturated fatty acid at a double bond portion. Dimer acid mainly refers to dimer, but also includes the concept of trimer, tetramer and other polymers. Furthermore, even if a monomer of a monounsaturated fatty acid is used, copolymerization accompanying the esterification reaction is not performed, so that it is impossible to form a skeleton of a polymer chain constituting a polyester, and a desired effect cannot be obtained. One kind of dimer acid can also be used, but it is usually obtained in the form of a mixture of two or more kinds, so it is often used in various forms as a mixture. For example, a dimer acid can be obtained by dimerizing a linear or branched unsaturated fatty acid having 8 to 22 carbon atoms. In the present invention, an unsaturated or saturated dicarboxylic acid obtained by partially or completely hydrogenating an unsaturated bond of a dimer acid, that is, a hydride of a dimer acid (hereinafter, referred to as "hydrogenated dimer acid") is also included in The concept of dimer acid. The hydrogenated dimer acid is preferred for reasons of being superior in heat resistance or colorless transparency compared to the dimer acid before hydrogenation.

Examples of the unsaturated fatty acid include fatty acids having 8 to 22 carbon atoms having 1 to 4 ethylenic double bonds, and fatty acids having 14 to 22 carbon atoms having 1 or 2 ethylenic double bonds are preferred.

Specific examples of the unsaturated fatty acid include octenic acid, undecylenic acid, tetradecadienoic acid, hexadecadienoic acid, octadecadienoic acid (such as linoleic acid), and Carbadienoic acid, docosadienoic acid, octadecadienoic acid (hypolinolenic acid, etc.), eicosatetraenoic acid (arachidonic acid, etc.), tetradecenoic acid (crude acid , Spermic acid, myristic acid), hexadecenoic acid (palmitoleic acid, etc.), octadecenoic acid (oleic acid, oleic acid, isoleic acid, etc.), eicosenoic acid (cocoic acid Etc.), docosaenoic acid (erucic acid, cetylenoic acid, barcol Cenoic acid, etc.) and so on. These can be used alone or in combination of two or more. In addition, the dimer acid may be made from a tall oil fatty acid, a soybean oil fatty acid, a palm oil fatty acid, a rice bran oil fatty acid, a linseed oil fatty acid, or the like as a mixture of unsaturated fatty acids.

Dimerization reactions are well-known, for example, liquid or solid catalysts of the Lewis acid or Bronsted acid type, preferably montmorillonite-based clay, can be used as the catalyst at a high temperature of about 200 to 270 ° C. The reaction was performed under the conditions. The dimer acid obtained is usually a mixture of dimer acids with different structures due to the bonding site or isomerization of the double bond, which can be used after being separated, but can also be used directly as a mixture. Furthermore, the obtained dimer acid may also contain a small amount of a monomer acid (for example, 6% by mass or less, especially 4% by mass) or a polymer acid of a trimer acid or more (for example, 6% by mass or less, especially 4% by mass or less).

Examples of the dimer acid include a chain dimer acid represented by the following structural formula (1).

In addition to the chain dimer acid represented by the above structural formula (1), a cyclic dimer acid represented by the following structural formula (2) or (3) or a mixture containing the same can also be dimerized. Obtained by reaction.

[Chemical 3]

Industrially available dimer acids include, for example, HARIDIMER 200, 300 (manufactured by Harima Kasei Co., Ltd.), TSUNODIME 205, 395 (manufactured by Chino Food Industry Co., Ltd.), and EMPOL (registered trademark) 1008, 1012 1026, 1028, 1061, and 1062 (manufactured by Cognis) include hydrogenated dimer acids such as Dimer acid hydrogenated (manufactured by ALDRICH), PRIPOL (registered trademark) 1009 (manufactured by Croda), and the like.

In another preferred embodiment of the present invention, the aromatic polyester resin has at least one of the aliphatic diol residue having the carbon number of 10 or more and the alicyclic diol residue having the carbon number of 10 or more as the Dimer diol residues. Dimer diol can be obtained by reducing the carboxyl group of the dimer acid.

Representative examples of dimer diols are PRIPOL (registered trademark) 2033 (manufactured by Croda), KX-501 (manufactured by Arakawa Chemical Industries), Sovermol (registered trademark) 650NS (manufactured by BASF), Sovermol 918 (manufactured by BASF) Manufacturing) etc.

From the viewpoint of imparting excellent softness and transparency to the waterproof coating film, the total number of acid component residues and total diol component residues in the above-mentioned aromatic polyester resin is the aliphatic carbon number of 10 or more. Dicarboxylic acid residues, alicyclic dicarboxylic acid residues having 10 or more carbon atoms, aliphatic diol residues having 10 or more carbon atoms, and alicyclic diol residues having 10 or more carbon atoms are contained in total. The ratio is preferably 0.5 mol% or more, more preferably 1 mol% or more, and even more preferably 2 mol% or more. Since the waterproof coating film has flexibility, it is possible to prevent the texture of the zipper chain cloth from being damaged or the sliding property of the slider from being deteriorated. Because the waterproof coating film has transparency, it will not damage the beauty of the zipper chain cloth like the previous polyester waterproof coating film.

However, if the content ratio of the residue having 10 or more carbon atoms in the polyester resin is excessive, the heat resistance of the polyester resin is easily impaired. Therefore, from the viewpoint of imparting excellent heat resistance to the waterproof coating film, the total number of total acid component residues and total diol component residues in the above-mentioned aromatic polyester resin is the above-mentioned aliphatic two having a carbon number of 10 or more. Total content ratio of carboxylic acid residue, alicyclic dicarboxylic acid residue having 10 or more carbon atoms, aliphatic diol residue having 10 or more carbon atoms, and alicyclic diol residue having 10 or more carbon atoms It is preferably 8 mol% or less, more preferably 5 mol% or less, and even more preferably 4 mol% or less.

Common additives such as dyes, pigments, heat-resistant stabilizers, weather-resistant agents (such as ultraviolet absorbers), hydrolysis-resistant agents, antioxidants, and lubricants can be added to the polyester resin composition constituting the waterproof coating film as appropriate. Although the addition amount of each additive is not limited, it is usually 10 parts by mass or less with respect to 100 parts by mass of the polyester resin. For example, it may be 0.1 to 5 parts by mass, or 0.3 to 3 parts by mass. In addition, even if an additive is added, the ratio of the polyester resin in the polyester resin composition constituting the waterproof coating film is usually 60% by mass or more, typically 70% by mass or more, and more typically 80%. It can be set to 90% by mass or more, or set to 95% by mass or more, and can also be set to a range of 80 to 99% by mass.

A hydrolysis-resistant agent can be added to the polyester resin composition constituting the waterproof coating film, but the polyester resin composition of the present invention is particularly preferably a hydrolysis-resistant agent that does not easily deteriorate in heat resistance because of its high flexibility. Among them, based on the excellent compatibility with polyester, it is not easy to bleed out even in a high temperature and humid environment, it is not easy to turbid, and it is not easy to volatilize even at a high temperature of 200 ° C. It is particularly preferred to add it as a kind of hydrolysis resistance agent. Polycarbodiimide. Although the added amount of polycarbodiimide is not limited, if the added amount is too large, the heat resistance is liable to decrease. On the other hand, if the added amount is too small, it is difficult to obtain the effect of improving the hydrolysis resistance. 100 parts by mass of the resin is 10 parts by mass or less, and may be, for example, 0.1 to 5 parts by mass, or 0.3 to 3 parts by mass.

The polycarbodiimide system has a structure represented by (-N = C = N-) (carbodiimide Compounds), for example, can be produced by heating an organic isocyanate in the presence of a suitable catalyst and using a decarboxylation reaction. Polycarbodiimide having a number average molecular weight of 8000 or more is preferably used. The number average molecular weight of the polycarbodiimide can be used by dissolving the polycarbodiimide powder in a member selected from the group consisting of chloroform, tetrahydrofuran (THF), and N-methyl-2-pyrrolidone (NMP ) And hexafluoroisopropanol (HFIP) as a single solvent or a mixture of two or more solvents, and the curve of the molecular weight distribution curve was measured using GPC (Gel Permeation Chromatography, gel permeation chromatography). Standard.

If the number average molecular weight of the polycarbodiimide is less than 8000, the volatility becomes large, so the degree of reduction of the reaction rate constant becomes small. The upper limit of the number average molecular weight of the polycarbodiimide is not particularly limited as long as the effect of the present invention is not impaired, but it is preferably 30,000 or less from the viewpoint of the mobility of the polymer chain. The number average molecular weight of the polycarbodiimide is preferably 8,000 to 30,000, and more preferably 8,000 to 15,000 from the viewpoints of volatility and mobility of the polymer chain.

The polycarbodiimide may be selected from compounds obtained by polymerizing an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, or a mixture thereof. Specific examples of the polycarbodiimide include poly (1,6-hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodiimide), and Poly (1,3-cyclohexylcarbodiimide), poly (1,4-cyclohexylcarbodiimide), poly (4,4'-dicyclohexylcarbodiimide), Poly (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthyl) Carbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropyl) Carbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, poly (1, 3,5-triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide, poly (triethylphenylene diimide), poly (triisopropylphenylene) Polycarbodiimide and the like. As a commercially available product, Rhein Chemie Japan Co., Ltd. can be used. "Stabaxol", etc. Specifically, examples of the polycarbodiimide include Stabaxol P (number average molecular weight 3000-4000, manufactured by Rhein Chemie), LA-1 (number average molecular weight about 2000, manufactured by Nisshinbo Chemical Co., Ltd.) Stabaxol P100 (number average molecular weight about 10,000, manufactured by Rhein Chemie), Stabaxol P400 (number average molecular weight about 20,000, manufactured by Rhein Chemie). Among them, polycarbodiimide having a larger number average molecular weight, such as Stabaxol P100 and Stabaxol P400, is preferred.

In addition, the polyester resin composition of the present invention contains an aromatic polyester resin having an aliphatic dicarboxylic acid residue having 10 or more carbon atoms, and thus tends to have relatively high adhesiveness. Therefore, in order to improve the sliding property between the slider and the waterproof coating film, in order to reduce the adhesiveness of the polyester resin composition, it is easy to blend in the production of the composite, and further, to make the zipper chain coated with the waterproof coating film. It is also preferable that a lubricant is added to the polyester resin composition constituting the waterproof coating film without sticking to each other. Although the amount of the lubricant added is not limited, if the amount of the lubricant is too large, bleeding may occur. On the other hand, if the amount of the lubricant is too small, the desired effect may not be obtained easily. Therefore, it is usually 10 parts by mass with respect to 100 parts by mass of the polyester resin. The content may be 0.1 to 5 parts by mass, or 0.3 to 3 parts by mass, for example.

Examples of the lubricant include synthetic resin-based lubricants (fluorine-based resins, acrylic resins, etc.), paraffin-based lubricants (natural paraffin, synthetic paraffin, etc.), and higher fatty acid-based lubricants (stearic acid, montanic acid, etc.) ), Ester lubricants (fatty acid esters, aromatic esters, etc.), fatty acid ammonium lubricants (ammonium sinarate, ammonium stearate, etc.), and the like. These lubricants may be used alone or in combination of two or more. Among these, a fatty acid ammonium-based lubricant is preferred for reasons of excellent sliding properties.

In order to prevent yellowing due to sunlight, it is particularly preferable to add an ultraviolet absorber to the polyester resin composition constituting the waterproof coating film. Although it is not limited as an ultraviolet absorber, an indole type, a three Type, benzotriazole type, benzophenone type, benzoate type, cyanoacrylate type, and phenylsalicylate type, and they may be used alone or in combination of two or more kinds. Among these, a benzotriazole-based ultraviolet absorber is preferred for reasons of excellent stability under high temperature and humidity and less coloring due to addition.

In addition, as the ultraviolet absorber, a pigment having a hiding power (light scattering property) can be added. Although there is no particular limitation, since the color tone and concealing power (light scattering property) are particularly excellent, inorganic white pigments such as titanium oxide, inorganic pigments having reflective properties, and black pigments such as carbon black can be preferably used. By adding the pigment of the same color as the chain cloth of the fastener, it becomes a fastener with high-quality appearance, so it is better. Particularly good is to mix red, blue, and yellow pigments with inorganic white pigments, and add pigments with the same color as the zipper chain.

Examples of the inorganic white pigment include ZnO, TiO ₂ and Al ₂ O ₃ . nH ₂ O, [ZnS + BaSO ₄ ], CaSO ₄ . 2H ₂ O, BaSO ₄ , CaCO ₃ , 2PbCO ₃ . Pb (OH) ₂ and the like. Among the inorganic white pigments, titanium oxide (TiO ₂ ) is preferred because it is particularly excellent in color tone and concealing power (light scattering properties) and can contribute to improvement of color tone and reflection characteristics of a white resin film. Titanium oxide is widely used in the two crystal forms of anatase type and rutile type. In the present invention, those two types of crystal forms can be used, but among them, those having a crystalline shape of rutile are preferable in terms of excellent dispersibility to the aromatic polyester resin and extremely low volatility. Titanium oxide.

As the titanium oxide, a pigment grade can be preferably used. The average particle diameter (average primary particle diameter) of titanium oxide obtained by image analysis of images taken with a transmission electron microscope is usually in the range of 150 to 1000 nm, preferably 200 to 700 nm, and more preferably 200 to 400 nm. If the average particle diameter of titanium oxide is too small, the hiding power will decrease. Titanium oxide has a large refractive index and a strong light scattering property because its average particle diameter is within the above range, so its hiding power as a white pigment becomes high. Titanium oxide generally exists in the form of secondary particles formed by agglomeration of primary particles. The specific surface area of the titanium oxide obtained by the BET (Brunauer-Emmett-Teller) method is usually 1 to 15 m ² / g, and in most cases, it is in the range of 5 to 15 m ² / g.

The black pigment is preferably carbon black. The carbon black is not particularly limited, and furnace black, chimney black, acetylene black, hot carbon black, and the like can be used, and carbon black obtained by surface modification by a carboxyl group or the like can also be used. The average particle diameter (average primary particle diameter) of carbon black obtained by image analysis of images taken with a transmission electron microscope is usually in the range of 10 to 150 nm, preferably 13 to 100 nm, and more preferably 15 to 40 nm. If the average particle diameter of the carbon black is too small, aggregation may easily occur, and handling may become difficult. If the average particle diameter is too large, it may cause poor dispersion or poor appearance. The use of carbon black obtained from BET specific surface area is generally 20 ~ 250m ² / g, preferably 50 ~ 200m ² / g, more preferably in the range of 80 ~ 200m ² / g of.

Although the addition amount of the ultraviolet absorber is not limited, if the addition amount is too large, bleeding will easily occur. On the other hand, if the addition amount is too small, the desired effect will not be easily obtained. Therefore, it is usually relative to 100 parts by mass of the polyester resin. 10 parts by mass or less may be, for example, 0.1 to 5 parts by mass, or 0.3 to 3 parts by mass.

Since the waterproof coating film of the present invention contains a polyester resin composition, the dyeing is also easy. For example, it can be colored into various colors by inkjet dyeing. In addition, since the water-repellent coating film of the present invention has high transparency, it is easier to control the color tone by coloring.

The polyester resin composition used for the waterproof coating film preferably has a melt viscosity at 200 ° C of 50 to 3000 dPa. s range so that it can be extruded from the die for curtain coating. By setting the melt viscosity at 200 ° C to 50dPa. s or more, preferably set to 100dPa. s or more, more preferably 200dPa. At least s, it is possible to prevent the flow rate of the molten resin from becoming excessive and detaching from the width of the fastener chain cloth, and to improve the film thickness controllability. In addition, the melting viscosity at 200 ° C was set to 3000 dPa. Below s, it is preferably set to 2000dPa. Below s, more preferably 1000dPa. Below s, it is possible to prevent the flow rate from becoming too small to slow down the formation of the coating film, and to prevent an increase in the load on the extruder or the mold. Furthermore, it is possible to suppress the effect of the resin on the zipper chain cloth during curtain coating. Press.

The melt viscosity can be controlled by adjusting the molecular weight. The melt viscosity can also be controlled by the structure of the acid component and the diol component constituting the polyester resin. If the composition The more the middle branch structure, the lower the melt viscosity. If the longer linear structure is more, the melt viscosity will be increased.

In the present invention, the melt viscosity is measured by the following method. The sample was heated at 200 ° C. for 15 minutes in advance, and the viscosity was measured at 200 ° C. using a B-type viscometer in accordance with JIS K7117-1 (1999).

Referring to FIGS. 1 to 3 again, the waterproof coating film 19 may extend along the long side direction and the short side direction of the fastener chain cloth 18 to cover the entire main surface. In the embodiment shown in the figure, the outer surface of the waterproof coating film 19 is at least flat through a predetermined portion thereon. This is to make the sliding of the sliding member 12 smooth. The outer surface of the waterproof coating film 19 at a portion where the slider 12 does not pass may also have a concave-convex shape, but from the viewpoint of ease of manufacture or aesthetic appearance, it is preferable to make the entire outer surface of the waterproof coating film 19 flat.

In order to effectively exert the waterproof function, it is preferable that the side on which the waterproof coating film 19 is formed is set to the outside, and the rows of the fastener elements 11 are set to the inside to be attached to the article. From the viewpoint of ease of opening and closing operations, the pull tab 15 of the slider 12 is preferably mounted on the outside.

In the illustrated embodiment, the end edges of the waterproof coating film 19 formed on the main surface of each zipper chain cloth 18 are close to each other from the above-mentioned one side edge of each zipper chain cloth 18 with the zipper chain closed. The direction extends and abuts. Thereby, waterproofness can be ensured. The edges of the waterproof coating film 19 abut against each other near the meshing centerline A of the row of the sprocket 11, thereby obtaining the advantage of smooth sliding of the slider 12.

From the viewpoint of improving abrasion resistance or scratch strength, the thickness of the waterproof coating film 19 is preferably 50 μm or more, and more preferably 100 μm or more. From the viewpoint of preventing the softness of the zipper chain cloth from being lowered and preventing the outer surface from being depressed due to impact, the thickness of the waterproof coating film 19 is preferably 350 μm or less, more preferably 300 μm or less, and even more preferably It is 200 μm or less.

In the present invention, the thickness of the waterproof coating film 19 is measured by the following method. First of all, it should be separated by 20mm or more in the long direction and 5mm or more in the width direction. At intervals, cut out 16 5mm square samples from the zipper chain. A microfocus X-ray fluoroscopy / CT (Computed Tomography) device (eg, "SMX225CT" manufactured by Shimadzu Corporation) was used to photograph the cut-out sample. The measurement conditions of the microfocus X-ray fluoroscopy / CT apparatus are shown below.

SID (source to image receptor distance): 600mm (distance from X-ray tube to X-ray detector)

SOD (source to object distance): 22.8mm (distance from the X-ray tube to the center of the turntable)

VOXEL SIZE: 0.012mm

X-ray tube voltage: 90kV

X-ray tube current: 40μA

Number of frames: 1200

Average: 10

Slice thickness: 0.013mm

Image size: 512 × 512pixel (pixels)

The microfocal X-ray fluoroscopy / CT device includes an X-ray tube that emits X-rays, an X-ray detector that detects X-rays, and a rotating table for placing and rotating a measurement object. Based on the CT image obtained by shooting, the thickness of the waterproof coating film was measured at three locations at 1 mm intervals in the longitudinal direction of the zipper chain, and the average value was calculated. This processing was performed on the 16 samples cut out, and the average value of the 16 samples was set as the measurement value of the thickness of the waterproof coating film.

(1-2. Zipper chain cloth)

The material of each of the fastener chain cloths 18 may be natural fibers or synthetic fibers generally used in fastener chain cloths. Although not particularly limited, examples thereof include polyamide resin fibers, polyester resin fibers, and acrylic resin fibers. Wait. Zipper chain fabrics can be produced by weaving or knitting these synthetic fibers. In terms of improving recyclability, polyester is preferably used. Resin fiber.

As the polyester resin for the fastener chain cloth, any known material can be used as the polyester for the fastener chain cloth, but as the polyester resin for the fastener chain cloth, an aromatic polyester resin is also preferable. Specific examples of the polyester resin for a zipper chain cloth are selected from the group consisting of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate ( PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), or a combination thereof. Among these, a polyethylene terephthalate (PET) resin is preferable for the reason that both mechanical strength and dyeability are excellent. Common additives such as dyes, pigments, heat-resistant stabilizers, weather-resistant agents, hydrolysis-resistant agents, and antioxidants can also be added to polyester resins as appropriate.

It is also possible to perform water repellent processing on one or more of the core rope, the suture, the sprocket and the zipper chain cloth. As a method of water-repellent processing, the method of attaching a water-repellent agent to the surface of a target component is mentioned. For the fastener chain cloth, a water-repellent agent can be attached to the waterproof coating film.

As the water-repellent agent, a fluorine-based compound, a polysiloxane-based compound, an acrylic-based water-repellent agent, a polysiloxane-based composite water-repellent agent, a paraffin-based compound, an ethylene urea-based compound, a zirconium-based compound, and a fatty acid amidine Water-repellent agents such as system compounds, hydroxymethyl amidamine-based compounds, alkylurea type, and fatty acid amidamine type.

As the water-repellent agent of the above-mentioned fluorine-based compound, polypentafluorooctyl acrylate, polytrifluoroethyl acrylate, tetrafluoroethylene-hexafluoropropylene copolymer, etc., or perfluorolauric acid, polytetrafluoroethylene, Perfluoron-alkyl acrylate, polyvinylidene fluoride, pentabutyl ethyl methacrylate, hexafluoropropylene, etc.

In addition, as a water-repellent agent for other fluorine-based compounds, copolymers containing two or more kinds of olefins containing fluorine atoms, copolymers of olefins containing fluorine atoms, and hydrocarbon monomers can be used. Furthermore, in terms of improving the durability of water repellency, the water repellent is preferably provided to the knitted fabric together with the binder resin.

As the polysiloxane compound, polydimethylsiloxane, methyl hydrogen polysiloxane can be used. Various modified polysiloxanes such as oxane, amine modified, epoxy modified, carboxyl modified, quaternary ammonium salt modified, higher alkyl modified, fluorine modified, or polyhydrogen containing methyl hydrogen A polysiloxane-based water repellent treatment agent for the hardening and promotion of aromatics such as toluene, xylene, n-hexane, n-heptane and the like. Polysiloxane based water repellent has the following advantages: (1) large contact angle with water, excellent water repellency; (2) small surface tension, so it is easy to wet the substrate, can form a uniform film; (3) It has air permeability; (4) Good durability, excellent washing resistance and dry cleaning resistance.

As the polysiloxane-based water-repellent agent, an anionically stabilized organic polymer containing a hydroxyl group as described in Japanese Patent Laid-Open No. 58-118853 or Japanese Patent Laid-Open No. 60-96650 can be used. Siloxane, colloidal silicon oxide, and polysiloxane emulsion of hardening catalyst, or ionic or non-ionic stabilized organic polymer containing alkoxy group described in Japanese Patent Laid-Open No. 7-150045 Silicone emulsions such as silicone and titanium catalysts are room-temperature-curable aqueous silicone emulsion compositions and the like that harden at room temperature by removing moisture and give elastomeric hardened materials.

In order to improve the durability of the water-repellent agent, a cross-linking agent may be used in combination with the above compounds. As the crosslinking agent, a melamine-based resin, a blocked isocyanate-based resin, an imine-based resin, or the like can be used.

In order to improve the durability of the water-repellent agent, the compound and the binder resin may be contained. As the binder resin, an acrylic resin, a urethane resin, a silicone resin, or the like can be used.

Regarding the cross-linking agent or the binder resin, the two may be mixed and used. In this case, the polyfluoroalkyl-containing acrylic copolymer and the amine-based plastic resin may be used as the treatment liquid, or the polyfunctional end-capping may be used. It is used in the form of a mixed solution of an isocyanate urethane resin.

(2. Manufacturing method of zipper chain)

Next, an example of the manufacturing method of the fastener chain of this invention is described, referring FIG. First, a zipper chain 21 is prepared. The zipper chain 21 includes a pair of zipper chain cloths, One of the side edges is adjacent to each other at a specified interval; and a sprocket row is mounted on the main surface of the above-mentioned one side edge of each zipper chain cloth. The description of the members constituting the zipper chain 21 is as described above.

Then, the polyester resin composition 22 having a melt viscosity at 200 ° C in the above range was extruded at the exit of the die 23 at 150 to 250 ° C, and the polyester resin composition 22 was curtain-coated on each zipper chain cloth. On the main surface opposite to the main surface on which the sprocket row is mounted and on the interval (s). The polyester resin composition can be extruded, for example, by a conventional extrusion molding method using an extruder 24 and a die 23. The reason for setting the melt viscosity of the polyester resin composition 22 at 200 ° C is as described above. The temperature of the polyester resin composition 22 at the exit of the mold 23 is set to 150 ° C. or higher in order to set the resin composition to a viscosity capable of being applied. The temperature of the polyester resin composition at the die exit is preferably 170 ° C or higher, and more preferably 190 ° C or higher. The temperature of the polyester resin composition at the exit of the mold is set to 250 ° C. or lower in order to prevent thermal degradation of the resin composition. The temperature of the polyester resin composition at the die exit is preferably 230 ° C or lower, and more preferably 210 ° C or lower.

The polyester resin composition is preferably applied to the main surface of the fastener chain cloth by curtain coating. The polyester resin composition immediately after being discharged from the die exit has a high temperature and relatively high fluidity. Therefore, if the polyester resin composition is pressed into the zipper chain cloth at a relatively high pressure, the polyester resin composition is likely to be installed on a pair of zipper. The gap (s) between chain cloths enters. If the polyester resin composition enters the gap too much, there is a possibility that a contact with the slider may occur, and the waterproof coating film may be damaged due to sliding with the slider.

In view of this aspect, in the case of curtain coating, the molten polyester resin composition discharged from the die outlet can be reduced to the main surface of the zipper chain cloth after the pressure at the time of discharge is released into the air, so that it can be reduced. The self-pressing polyester resin composition presses the main surface of the zipper chain cloth. Thereby, it is possible to prevent the polyester resin composition from entering the gap caused by the interval (s) provided between the pair of fastener chain cloths to an inappropriate degree.

In addition, a curtain type is performed on a polyester resin composition having a specific melt viscosity. By coating, a polyester resin composition of a desired shape and size can be laminated on a zipper chain cloth. Therefore, it can be coated with a desired thickness or width according to the shape and size of the die exit, and can also be coated in a strip shape with a uniform thickness. It is advantageous in industrial production to carry out curtain coating while transporting the zipper chain along its long side.

The die exit preferably extends across the entire width direction of the pair of zipper chain cloths. This makes it possible to form a waterproof coating film without interruption in the width direction of the chain cloth on the main surfaces of the pair of fastener chain cloths. The thickness of the polyester resin composition applied to the fastener chain can be controlled by adjusting the slit width (w) at the die exit. For reasons of maintaining the strength of the resin layer, the slit width (w) is preferably 0.01 mm or more, more preferably 0.05 mm or more, and even more preferably 0.1 mm or more. In addition, in order to prevent an increase in weight and a decrease in flexibility caused by the thickening of the resin layer, the slit width (w) is preferably 0.8 mm or less, more preferably 0.4 mm or less, and even more preferably 0.25. mm or less.

According to curtain coating, the pressure of the polyester resin composition discharged from the die exit on the main surface of the zipper chain cloth can be set to 1 MPa or less. If the pressure is within this range, the polyester resin composition can be effectively suppressed. Deep into the gap between a pair of zipper chain. The pressure is preferably 0.8 MPa or less, and more preferably 0.5 MPa or less. However, if the pressure of the polyester resin composition discharged from the mold outlet on the main surface of the zipper chain cloth is too small, the resin will not enter the fibers of the zipper chain cloth, thereby reducing the adhesion. Therefore, the pressure is preferably set to 0.1 MPa or more, more preferably 0.2 MPa or more.

In the present invention, the pressure is measured by providing a pressure gauge under the fastener chain cloth and continuously flowing the polyester resin composition, thereby measuring the pressure applied to the fastener chain cloth.

The pressure of the polyester resin composition discharged from the die exit on the main surface of the zipper chain cloth is as shown in FIG. 4, which can be adjusted from the die exit to the main surface of the zipper chain cloth coated with polyester resin by the curtain type. The distance (g) is controlled, and the distance (g) can be set to, for example, 0.1 to 2.0 mm. From the viewpoint of not contacting the mold with the fastener chain having unevenness on the surface, the distance (g) is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5mm or more. From the viewpoint of maintaining the shape after being discharged from the die exit, the distance (g) is preferably 2.0 mm or less, more preferably 1.5 mm or less, and even more preferably 1.0 mm or less.

As shown in FIG. 4, after the polyester resin composition 22 is curtain-coated on the main surface of the zipper chain cloth, the metal is heated from 100 to 250 ° C. from the coated surface side of the polyester resin composition. Between the roller 25 and the roller 26 having a hardness of 5 to 50 ° from the non-coated side of the polyester resin (zip fastener chain), the zipper chain 21 is pressurized at a pressure of 0.1 to 10.0 MPa while passing through it. Through this step, the polyester resin moderately enters the fine unevenness on the main surface of the zipper chain cloth, and the adhesion strength is improved by the anchor effect. This step is carried out continuously after the curtain-type coating, while carrying the zipper chain along its long side direction, which is advantageous in industrial production.

The reason for using the metal roller 25 on the side of the polyester resin composition coating surface is that it is excellent in mechanical strength, heat resistance, and smoothness, and the polyester resin composition applied to the fastener chain cloth is not easily adhered to the roller. By heating the roller 25 to 100-250 ° C, the polyester resin composition is softened and further enters the fine unevenness of the zipper chain cloth, thereby obtaining a stronger anchoring effect. For reasons of promoting softening of the polyester resin composition, the heating temperature of the roller 25 is preferably 120 ° C or higher, and more preferably 150 ° C or higher. From the viewpoint of preventing thermal degradation of the polyester resin composition, the heating temperature of the roller 25 is preferably 220 ° C or lower, and more preferably 200 ° C or lower.

By using a soft roller 26 having a hardness of 5 to 50 ° on the non-coated side (zip chain cloth) side of the polyester resin composition, the surface of the roller will follow the main surface of the zipper chain cloth when the zipper chain passes the roller The fine unevenness is deformed, so that the adhesion between the polyester resin and the fastener chain can be further promoted, thereby reducing the defective portion of the adhesion. The reason why the hardness of the roll is set to 5 ° or more is to prevent plastic deformation caused by the roll being too soft, preferably 7 ° or more, and more preferably 10 ° or more. The reason why the hardness of the roll is set to 50 ° or less is to prevent the follow-up of fine unevenness due to the roll being too hard, preferably 40 ° or less, and more preferably 30 ° or less. As having this The hardness of the material in this range is not limited, and examples thereof include polysiloxane resin, Teflon resin, rubber roller, and the like. For reasons of continuous softness over a long period of time, polysiloxane resin is preferred.

In the present invention, the hardness of the roll is measured by the following method. According to JIS K6253 (2006), the hardness was measured by pressing a durometer against the surface of the roller.

It is not necessary to heat the roller 26 on the non-coated surface (zip fastener chain) side of the polyester resin composition. The reason is that if the roller on the side of the zipper chain cloth is heated, the chain cloth is directly heated because the resin is not coated, so it is considered that the zipper chain cloth itself may be thermally deformed.

From the viewpoint of reliably bringing the roller and the coating surface of the resin composition into close contact, the pressure when the zipper chain coated with the polyester resin composition passes between the rollers is preferably set to 0.5 MPa or more, and more preferably It is 1.0 MPa or more, and more preferably 1.5 MPa or more. From the viewpoint of preventing leakage of the resin layer due to excessive pressure, the pressure is preferably 10 MPa or less, more preferably 5 MPa or less, and even more preferably 2 MPa or less.

In the present invention, the pressure at the time of passing the roller is the pressure of pressing the resin composition-coated side roller against the non-coated surface side roller of the resin composition with the zipper chain cloth sandwiched between the rollers. According to JIS B7505 (1999 ) To measure the pressure.

Then, the polyester resin on the zipper chain is cooled and hardened, so that the waterproof coating film is firmly fixed on the main surface of the zipper chain. As a cooling condition, the surface of the chain cloth may be cooled by blowing air. When the resin is rapidly cooled, it may cause excessive deformation due to shrinkage. Therefore, for reasons of preventing the excessive deformation, the wind speed at this time is preferably 30 m / s or less, more preferably 20 m / s or less, and more preferably It is 10 m / s or less. This cooling step is also carried out continuously while carrying the zipper chain along its long side after the roller is pressurized, which is advantageous in industrial production.

In the present invention, the wind speed is measured by an anemometer according to JIS T8202 (1997).

Thereafter, the waterproof coating film formed on the interval (s) of the fastener chain is cut between the intervals. It is preferable to cut along the center line A of the interval. To cut off, just use e.g. A slitter (not shown) is sufficient. This cutting step is also carried out continuously while carrying the zipper chain along its long side direction, which is advantageous in industrial production.

The zipper of the present invention can be used not only for opening and closing parts of daily necessities such as clothing, bags, footwear, and miscellaneous goods, but also for space suits, chemical protective suits, diving suits, lifeboats, life jackets, etc. Protective clothing, protective covers for transport containers or tents.

Examples

In order to better understand the present invention and its advantages, examples are shown below, but the present invention is not limited to these examples.

<Test Example 1>

(1.Production of polyester resin)

To a two-liter three-necked flask equipped with a stirrer, a condenser, and a thermometer, a terephthalic acid (TPA) and isophthalic acid (IPA) as dicarboxylic acids were added at a mixing ratio corresponding to each test number described in Table 1. ), Dimer acid (DA), adipic acid (AA), sebacic acid (SA), hydrogenated dimer acid (H-DA), 1,6-naphthalenedicarboxylic acid (NDCA), and 1,12-ten Diethylene glycol (DDA), ethylene glycol (EG), 1,2-propylene glycol (PG), 1,4-butanediol (1,4-BG), and diethylene glycol (DEG) as glycols , 1,4-cyclohexanedimethanol (CHDM), 1,12-dodecanediol (DMG), 4-hydroxymethylcyclohexanepropanol (HCHP), 4-hydroxymethylcyclohexane isopropyl Propylene alcohol (HCHIP), dimer diol (DG) and hydrogenated dimer diol (H-DG), a small amount of tetraisopropyl titanate as a catalyst, are heated while stirring to 180 ° C, and then carried out while While stirring, the temperature was gradually raised from 180 ° C to 240 ° C, and an esterification reaction was performed at 240 ° C for 5 hours under normal pressure. Thereafter, the pressure in the flask was gradually decreased to 133 Pa (1torr), and after reaching 133 Pa, a reaction was performed for 5 hours, thereby obtaining a high-viscosity caramel-like polyester resin (P) having various resin compositions described in Table 1. -1 ~ P-27).

The dimer acid (DA), hydrogenated dimer acid (H-DA), dimer diol (DG), and hydrogenated dimer diol (H-DG) used here are the following.

Dimer acid (DA): HARIDIMER200 (the carbon number of the main component is 36, manufactured by Harima Chemical Co., Ltd.)

Hydrogenated dimer acid (H-DA): PRIPOL1009 (the carbon number of the main component is 36, manufactured by Croda)

Dimer diol (DG): Reduced carboxyl group of HARIDIMER200

Hydrogenated dimer diol (H-DG): reduced product of carboxyl group of PRIPOL1009

(2. Production of composite of polyester resin composition)

The synthesized polyester resin has rubber elasticity and cannot be pulverized by a pulverizer at normal temperature. Therefore, the synthesized polyester resin is mixed with dry ice, put into the pulverizer, frozen and pulverized, and then dried to prepare a polyester resin. Powder. Then, a ratio of 100 parts by mass of the polyester resin described in Table 2 to polycarbodiimide: 0.5 parts by mass, an ultraviolet absorber: 0.5 parts by mass, and a lubricant: 1.0 parts by weight was performed with a blender. Dry blending to produce a composite of polyester resin composition. The additives used are as follows.

Polycarbodiimide: Rhein Chemie, trade name "Stabaxol P-100" (hereinafter referred to as "P-100")

Lubricant: Made by Kao Corporation under the trade name "Fattamine S" (hereinafter referred to as "Samine S")

Ultraviolet absorber (benzotriazole series): Chemipro Chemical Co., Ltd., trade name "KEMISORB73" (hereinafter referred to as "KEMISORB73")

(3. Production of zipper chain)

For each test example, two long polyester resin zipper chain cloths with a chain width of 16.5 mm and a chain cloth thickness of 0.6 mm were prepared, and a polyester resin hoop-shaped chain was sewn on the side edge of each zipper chain cloth. The teeth row and the opposite teeth row are engaged to form a zipper chain.

(4. Production of zipper chain: formation of waterproof coating film by curtain coating)

A white and black zipper chain that is fed with the composite of the polyester resin composition produced above into a curtain-type coating device having the structure shown in FIG. 4 is transported along the long side. The polyester resin composition (waterproof coating film) was continuously applied on the upper surface. At this time, the conveying speed of the zipper chain is set to 10m / min, the temperature at the mold exit is set to 200 ° C (the melt viscosity of any resin composition at 200 ° C is about 500 ~ 800dPa · s), and the slit at the mold exit The width (w) was set to 33 mm. In addition, the distance (g) from the die exit to the main surface of the zipper chain cloth was set to 1.0 mm, the discharge amount of the polyester resin composition was set to 250 g / min, and the resin composition was applied to the main surface of the zipper chain cloth during curtain coating. The pressure was set to 0.4 MPa. After coating, the polyester resin composition was cooled and hardened by blowing air on the surface of the fastener chain at a wind speed of 10 m / s. Finally, the surface of the zipper chain cloth opposite to the side coated with the waterproof coating film, including the surface of the ring-shaped fastener element row, is coated with a fluorine water-soluble water-repellent agent by a roller coater. And allowed to dry to obtain a white and black zipper chain (F-1 to F-28) with a thickness of about 120 to 140 μm.

(5. Characteristic evaluation of zipper chain)

Each characteristic of the zipper chain obtained in the above-mentioned manner was evaluated.

(1) Softness test

FIG. 8 shows a state before the flexibility test device 50 is operated. FIG. 9 shows a state in which the flexibility test device 50 is operated to press the fastener chain. The test sample 60 of the zipper chain with a diameter of 120 mm or more is in a state where the sprockets are meshed, and the hoop sprocket becomes the inside, and is bent into a ring near the center to form a ring portion 60a, and overlapping portions 60b are formed at both ends. . The length of the ring portion 60a is set to 80 mm, and the length of the overlapping portion 60b is set to 20 mm or more. The overlapping portion 60b is preferably fixed by an adhesive tape or the like.

As shown in FIG. 8, a softness testing device 50 for a softness test includes: a moving member 51 that moves up and down; a load element 52 that is mounted on the moving member 51 and converts the load into an electrical signal; It is mounted on the load cell 52 to pressurize the ring portion 60a of the test sample 60; and a splint 54 to fix the overlapping portion 60b of the test sample 60.

The clamp plate 54 supports the test sample 60 in a state where the ring portion 60 a projects upward and sandwiches the overlapping portion 60 b. In this state, the moving member 51 moves downward. When the moving member 51 moves downward, the load cell 52 and the presser 53 also move downward. Then, as shown in FIG. 9, the pressure member 53 presses the ring portion 60 a. After the moving member 51 moves downward to a specific position, the tester detects the maximum load in the moving range by the load element 52. Five tests were performed on each test sample, and the respective average values were obtained.

(2) Reciprocating opening and closing test

According to JIS S 3015 (2007), a reciprocating opening and closing endurance test with 500 openings and closings was performed at MH level. With respect to the sample after the test, the appearance evaluation of the passing part (observation area 750 mm ² ) of the sliding member in the surface of the waterproof coating film was performed on the basis shown below. The evaluation criteria are as follows.

：: No scratches or sliding marks were observed at all.

○: Slight scratches or sliding marks were observed.

△: Scratches or sliding marks were observed.

×: Film peeling was observed.

Note: △ above is the level allowed as a product.

(3) Transparency

The black zipper chain was evaluated visually for the transparency immediately after production and after standing at room temperature for one week. The evaluation criteria are as follows. The color range of the black zipper chain before applying the waterproof coating film is calculated as L ^* a ^* b ^* (D65), which is L ^* = 19.0 ~ 21.0, a ^* =-1.0 ~ 1.0, b ^* =-1.0 ~ 1.0.

(Double-circle): It is transparent, and whitening was not recognized at all.

○: Slight whitening was confirmed locally.

△: Although slight whitening was confirmed as a whole, there was no problem in practical use.

×: Significant whitening was recognized, which was a practical problem.

(4) Colorability

White for the fastener chain, the fastener chain of the white before the b ^* waterproof coating is applied as a reference difference was measured △ b ^*. The color range of the white zipper chain before coating with polyester resin is L ^* = 88.0 ~ 90.0, a ^* =-1.0 ~ 1.0, b ^* =-2.0 ~ 0.0 in terms of L ^* a ^* b ^* (D65). The color measurement system uses a spectrophotometer CM-3700A manufactured by Konica Minolta to measure a diameter of 5 × 7 mm, and performs reflection measurement of SCI (Specular Component Include, including specular specular reflection light). The chain cloth portion of the zipper chain was cut out, and 15 points were measured at an interval of 1 cm. The average value was set as the color difference Δb ^* as the colorability and classified into the following grades.

◎: less than 2.0

○: 2.0 or more and less than 3.0

△: 3.0 or more and less than 4.0

×: 4.0 or more

As long as it is less than 4.0, it will be a practical level.

(5) Water resistance test

According to the rain test B method (refer to Appendix JA of JIS L1092 (2009)), a water resistance test was performed. The fixing fixture of the sample of the produced zipper chain will be described using FIG. 5. Fig. 5 is a diagram showing a top view and a side cross-sectional view (a diagram viewed in the direction of the arrow A-A) of a fixing jig used for a test sample of the rain test B method.

As shown in FIG. 5, the fixing jig 30 includes an opening member 34 including an opening window for pouring water poured from above onto the test sample 36, and a water storage member 32 disposed below the opening member 34. And is provided with a storage section for storing the moisture transmitted through the test sample 36. The test sample 36 is used by being sandwiched between the opening member 34 and the water storage member 32. In order to prevent the test sample 36 from being submerged in water and maintain a specific inclination, the rain test was performed by using the angle fixture 38 and the fixing jig 30 at an angle of 45 degrees in the rain test B method. Moreover, the size of the opening window of the opening member 34 is as shown in FIG. 5, the window length is 200 mm, and the window width is 15 mm. The length of the test sample 36 was 250 mm.

FIG. 6 is a diagram showing the appearance of an artificial rainfall device when the rain test B method is implemented. The fixing jig 30 and the angle fixture 38 are shown in cross section. As shown in FIG. 6, the fixing jig 30 on which the test sample 36 is mounted is placed on the angle fixture 38 and set to an angle of 45 degrees. A spray nozzle 40 for watering is arranged at a position 2000 mm above the fixing jig 30. A water supply pipe 42 is connected to the spray nozzle 40, and water is sent to the inside under pressure. A water amount adjustment valve 44 that adjusts the water amount of the sprayed water is arranged in the middle of the pipe 42.

When the rain test B method is implemented, the test sample 36 is cut to a length of 250 mm, and the mass (M ₀ ) before the test is measured in advance. Then, the test sample 36 is sandwiched between a specific position between the opening member 34 and the water storage member 32. And, while preparing for the test after the end of the suction accumulated inside the water storage member 32 draws the paper through the measurement and quality of the water of the test sample 36, and draws the initial pre-metered as paper mass (M _1).

Next, the fixing jig 30 sandwiching the test sample 36 was placed on the angle fixture 38 and set at an angle of 45 degrees, and was arranged at a position of 2000 mm below the spray nozzle 40. Then, while observing the rain gauge, the water amount adjusting valve 44 was adjusted, and the rainfall was set to 100 mm / h. Then, the spraying of water to the fixing jig 30 was started, and the spraying was stopped after 15 minutes.

After the watering is finished, the test sample 36 is first removed from the fixing jig 30, and the mass (M ₂ ) of the test sample 36 after the test is measured. Further, the suction paper is dipped into the accumulated water 46 (see FIG. 7) accumulated inside the water storage member 32, and all the water accumulated inside the water storage member 32 is absorbed. Then, the mass (M ₃ ) after water absorption was measured.

Next, calculate the permeation amount (g) = (M ₂ -M ₀ ) + (M ₃ -M ₁ ), and calculate the permeation amount of water obtained by the rain test B method.

FIG. 7 shows a state in which water that has passed through the test sample 36 by watering is accumulated inside the water storage member 32 and water 46 is present. In addition, for convenience of explanation, the fixing jig 30 and the angle fixing tool 38 are shown in cross sections.

(Heat resistance)

The drying test was performed in accordance with JIS-L-0850 (1994) "Dry heat tester method (A-2 method) for dyeing fastness test against hot pressing". The chain cloth portion of the zipper chain was cut out as a test piece, and the test piece was placed so that the waterproof coating film became the cotton side of the test stand, and the heating portion set at 150 ° C. was overlapped at 4 kPa for 15 minutes. The test piece was left at room temperature until it became 30 ° C or lower. The test piece was peeled from the cotton cloth, and the area of the resin attached to the cotton cloth was measured. Five tests were performed and the average value was calculated.

Heat resistance (%) = adhesion area ÷ pressurized contact area × 100

* The smaller the value, the better the heat resistance.

<Test Example 2>

Except that the amounts and types of additives in the fastener chain F-13 of Test Example 1 were changed as described in Table 3, fastener chains F-31 to 47 were produced in the same order as the fastener chain F-13. However, the F-44 is a black zipper chain, and the other is a white zipper chain. The additives newly used in Test Example 2 are as follows.

<Additives>

Polycarbodiimide: manufactured by Nisshinbo Chemical Co., Ltd. under the trade name "LA-1" (number average molecular weight approximately 2000) (hereinafter referred to as "LA-1")

Polycarbodiimide: manufactured by Rhein Chemie, trade name "P-400" (number average molecular weight about 20,000) (hereinafter referred to as "P-400")

Ultraviolet absorber (benzophenone-based): manufactured by Chemipro Chemical Co., Ltd. under the trade name "KEMISORB10" (hereinafter referred to as "KEMISORB10")

Ultraviolet absorbent (pigment-based titanium oxide): manufactured by Dupont under the trade name "TI-PURE (registered trademark) R101" (hereinafter referred to as "R101")

Ultraviolet absorbent pigment (pigment-based carbon black): manufactured by Mitsubishi Chemical Corporation under the trade name "Carbon Black # 45" (hereinafter referred to as "# 45")

Lubricant (fluorine resin lubricant): manufactured by Kitamura Co., Ltd. under the trade name "KTL-450A" (hereinafter referred to as "KTL-450A")

About the obtained fastener chain, "colorability" and "heat resistance" were evaluated by the same method as Test Example 1. Furthermore, evaluations related to "exudation", "hydrolysis resistance", "light resistance", "light resistance after high temperature and humidity", and "sliding resistance" were performed by the methods described below. The results are shown in Table 4.

(Exudative)

The zipper chain was placed in a constant temperature and humidity tank at 70 ° C. and a relative humidity of 90%. After an exposure test for 1,000 hours, the surface of the zipper chain was observed to evaluate the presence or absence of bleeding.

◎: No bleed out on the surface at all; ○: Slight local bleed out was observed on the surface; △: Slight bleed out of the entire surface was slightly observed on the surface; X: bleed out of the entire surface was clearly observed on the surface.

(Hydrolysis resistance)

The zipper chain was placed in a constant temperature and humidity tank at 70 ° C and a relative humidity of 90%, and subjected to an exposure test for 1000 hours. The zipper chain after the test was subjected to a reciprocating opening and closing endurance test with 10 openings and closings in accordance with JIS S 3015 (2007) at MH level, and the appearance was evaluated.

◎ = No change at all.

○ = Local whitening was observed.

△ = Swelling of the local resin layer was observed.

× = Resin layer deteriorated and peeling was observed.

(Lightfastness)

For a white zipper chain, a light resistance test using a carbon arc lamp was performed in accordance with JIS-L-0842 (2004) (the third exposure method). B In the fastener chain before the light resistance test ^* as a reference, the color difference was measured △ b ^*. The color range of the white zipper chain before applying the waterproof coating film is L ^* = 88.0 ~ 90.0, a ^* =-1.0 ~ 1.0, b ^* =-2.0 ~ 0.0 in terms of L ^* a ^* b ^* (D65). The color measurement was performed using a spectrophotometer CM-3700A manufactured by Konica Minolta Co., Ltd. to measure a diameter of 5 × 7 mm and perform reflection measurement of SCI. The chain cloth portion of the zipper chain was cut out, and 15 points were measured at intervals of 1 cm ^. The average value of the color difference Δb ^* was set as light resistance, and was classified into the following grades.

For black zipper chain F-44, the same light resistance test as white is also performed. The color range of the black zipper chain before applying the waterproof coating film is calculated as L ^* a ^* b ^* (D65), which is L ^* = 19.0 ~ 21.0, a ^* =-1.0 ~ 1.0, b ^* =-1.0 ~ 1.0.

◎: less than 2.0

○: 2.0 or more and less than 3.0

△: 3.0 or more and less than 4.0

×: 4.0 or more

As long as it is less than 4.0, it will be a practical level.

(Light resistance after high temperature and humidity treatment)

The zipper chain was placed in a constant-temperature and constant-humidity tank at 70 ° C and a relative humidity of 90%, and an exposure test was performed for 1,000 hours. Then, the same light resistance test as described above was performed.

(Sliding resistance)

The sliding resistance was evaluated in accordance with JIS S 3015 (2007).

10‧‧‧ Zipper

11‧‧‧ sprocket

12‧‧‧ Slide

15‧‧‧ pull

16‧‧‧ Upper stop

19‧‧‧Waterproof coating

Claims (15)

A zipper chain has the following structure: a row of zipper fastener elements installed along respective side edge portions of a pair of zipper chain cloths with a waterproof coating film formed on at least one main surface is formed by mutual engagement; and the above waterproof coating film It is formed from a polyester resin composition containing an aliphatic dicarboxylic acid residue having 10 or more carbon atoms, an alicyclic dicarboxylic acid residue having 10 or more carbon atoms, and 10 or more carbon atoms. An aromatic polyester resin having one or two or more residues in a group consisting of an aliphatic diol residue and an alicyclic diol residue having a carbon number of 10 or more, wherein the above-mentioned aromatic polyester resin In the total of the total acid component residues and the total diol component residues in the above, the above-mentioned aliphatic dicarboxylic acid residue having a carbon number of 10 or more, the above-mentioned alicyclic dicarboxylic acid residue having a carbon number of 10 or more, and the above-mentioned carbon number The total content ratio of the aliphatic diol residues of 10 or more and the alicyclic diol residues of the above-mentioned carbon number of 10 is 0.5 to 8 mole%. The zipper chain of claim 1, wherein the aromatic polyester resin has at least one of the above-mentioned aliphatic dicarboxylic acid residues having 10 or more carbon atoms and the above-mentioned alicyclic dicarboxylic acid residues having 10 or more carbon atoms as two Polyacid residue. The zipper chain of claim 1, wherein the aromatic polyester resin has at least one of the aliphatic diol residues having a carbon number of 10 or more and the alicyclic diol residues having a carbon number of 10 or more as dimerization. Alcohol residue. The zipper chain according to claim 2, wherein the aromatic polyester resin has at least one of the aliphatic diol residue having a carbon number of 10 or more and the alicyclic diol residue having a carbon number of 10 or more as a dimer. Alcohol residue. The zipper chain of claim 2, wherein the dimer acid residue is a hydrogenated dimer acid residue. The zipper chain of claim 3, wherein the dimer diol residue is a hydrogenated dimer diol residue base. The zipper chain according to any one of claims 1 to 3, wherein the polyester resin composition contains a polycarbodiimide. The fastener chain according to any one of claims 1 to 3, wherein the polyester resin composition contains a lubricant. The fastener chain according to any one of claims 1 to 3, wherein the polyester resin composition contains at least one of an ultraviolet absorber and a pigment. The fastener chain according to any one of claims 1 to 3, wherein the content ratio of the aromatic polyester resin in the polyester resin composition is 60% by mass or more. The zipper chain according to any one of claims 1 to 3, wherein the zipper chain cloth is made of polyester resin. The zipper chain according to any one of claims 1 to 3, wherein the above-mentioned waterproof coating film enters the unevenness of the main surface of the zipper chain cloth at the interface with the zipper chain cloth. The zipper chain according to any one of claims 1 to 3, wherein the waterproof coating film is dyed. A zipper provided with the zipper chain according to any one of claims 1 to 13. An article provided with a zipper as claimed in claim 14.