CN108024602B - Slide fastener chain and slide fastener - Google Patents

Abstract

A slide fastener chain using a polyester resin material as a waterproof coating film has improved flexibility and transparency of the waterproof coating film. A fastener chain having a structure in which fastener element rows of fastener elements are engaged with each other, the fastener element rows being attached along each side edge portion of a pair of fastener tapes each having a waterproof coating film formed on at least one main surface thereof, the waterproof coating film being formed of a polyester resin composition containing an aromatic polyester resin having one or two or more residues selected from the group consisting of an aliphatic dicarboxylic acid residue having 10 or more carbon atoms, an alicyclic dicarboxylic acid residue having 10 or more carbon atoms, an aliphatic diol residue having 10 or more carbon atoms, and an alicyclic diol residue having 10 or more carbon atoms.

Description

Slide fastener chain and slide fastener

Technical Field

The present invention relates to a slide fastener. The invention particularly relates to a nylon zipper with a waterproof function.

Background

Slide fasteners are widely used as opening and closing tools for daily necessities such as clothing, bags, footwear, and miscellaneous goods, and are also used for protective clothing such as space suits, chemical protective clothing, diving suits, lifeboats, and life jackets, covers for transport containers, tents, and the like. In such special applications, the slide fastener is also required to have waterproofness.

Generally, a slide fastener is mainly composed of three parts: the slide fastener includes a pair of long fastener tapes, fastener elements which are coupling portions of the slide fastener attached along one side edge of each tape, and a slider which controls opening and closing of the slide fastener by coupling and separating the fastener elements. In order to impart waterproofness, there is known a slide fastener in which a synthetic resin film having waterproofness is attached to a fastener tape, and the synthetic resin films of the right and left fastener tapes are closely contacted with each other at the time of coupling to exert waterproofness.

For example, Japanese patent application laid-open No. 2002-525143 (patent document 1) describes that a water-resistant film such as a polyurethane film is attached to one surface of a fastener tape of a slide fastener by a transfer lamination method using a nip roller or a lamination roller. This publication describes that the film is preferably formed as a multilayer structure having an outer wear-resistant layer and an inner low-temperature-melting material. And records that: the wear-resistant layer is arranged, so that the wear resistance is improved, the friction coefficient is reduced, and the operation is easy; by embedding a part of the low-temperature melt layer in the material of the fastener tape, the adhesion strength between the film and the fastener tape is improved. It is also described to coat the polyurethane film with an inner layer consisting of a polyurethane adhesive, a bonding agent or a hot-melt adhesive.

Japanese patent publication No. TWI220106 (patent document 2) describes the following method: the PU sheet with the release paper is pressed by a roller device from above the fastener tape coated with the PU gel to bond the PU gel to the PU sheet, and thereafter, the PU sheet is thermoplastically bonded to the PU gel by heating to form a waterproof layer.

Japanese patent No. 4312171 (patent document 3) describes a method of forming a waterproof film by impregnating a liquid polyester synthetic resin-based waterproof material into a fastener tape structure.

Japanese examined patent publication No. 1-14168 (patent document 4) describes that synthetic rubber such as silicone rubber, butyl rubber, chloroprene rubber, and urethane rubber is applied to a fastener tape as a waterproof sealing material layer and then dried to adhere the tape.

Japanese patent No. 3580725 (patent document 5) describes that a laminated synthetic resin film composed of a low-melting-point resin layer and a high-melting-point resin layer is heated and pressurized so that the low-melting-point resin layer and a fastener tape surface are brought into opposed contact with each other, and is fused to at least one surface of a fastener tape of a slide fastener. Polyurethane-based resins and polyester-based resins are disclosed as materials for laminated synthetic resin films.

Japanese patent No. 5387912 (patent document 6) describes a method of extrusion molding a coating layer made of polyurethane, polypropylene, polyvinyl chloride, rubber thermoplastic material, or the like on the surface of a fastener tape. Specifically, the method comprises: a step of conveying the fastener tape to an extrusion molding die; and a step of forming a waterproof layer by extrusion molding a coating layer of a waterproof polymer on the surface of the fastener tape.

Japanese patent laying-open No. 2012 and 24579 (patent document 7) describes that a fin-shaped polymer material in which the fastener element side expands is applied to the surface of a fastener tape. It is also described that a coating of polymeric material is extruded onto the belt. Examples of the polymer material include thermoplastic elastomers such as polychloroprene, polyurethane elastomers, and polyester elastomers. According to this document, a pair of fin-shaped polymer materials are closed to each other at the closing time of the slide fastener, thereby achieving a liquid-tight state at the mating surfaces of the polymer materials.

Documents of the prior art

Patent document

Patent document 1: japanese Kohyo publication 2002-525143

Patent document 2: publication No. TWI220106

Patent document 3: japanese patent No. 4312171

Patent document 4: japanese examined patent publication (Kokoku) No. 1-14168

Patent document 5: japanese patent No. 3580725

Patent document 6: japanese patent No. 5387912

Patent document 7: japanese patent laid-open No. 2012 and 245254

In recent years, increasing awareness of environmental protection has been raised, and production of products with less environmental load has been demanded, but in conventional waterproof slide fasteners, since there is no awareness that the kind of waterproof film is the same as that of the resin used for the fastener tape, synthetic rubber such as polyurethane is mainly used as a material of the waterproof film, and the fastener tape is generally made of polyester. However, if a different kind of resin is used for the waterproof film and the fastener tape, there is a problem that recycling property becomes difficult.

In addition, in order to secure the adhesive strength, conventionally, there is a problem that the number of steps is increased and the manufacturing cost is increased in many cases because the film is coated with the adhesive and then attached to the fastener tape. Since the adhesive contains components harmful to the human body, there is also a problem that special training and installation of a special exhaust device are required at the time of manufacture.

Japanese patent No. 4312171 (patent document 3) describes a method of forming a waterproof film by impregnating a liquid polyester synthetic resin-based waterproof material substance into a fastener tape structure, and japanese patent laid-open No. 2012 and 245258 (patent document 7) also discloses a polyester elastomer as a polymer material for coating the surface of a fastener tape. However, when a waterproof film is formed using a polyester resin material, the waterproof film has poor transparency, and therefore, the appearance of the waterproof film is impaired. Further, since the waterproof film made of a polyester resin material has low flexibility, there are problems that the slidability of the slider is deteriorated and the texture of the fastener tape is lowered.

Disclosure of Invention

The present invention has been made in view of the above circumstances, and one of the objects of the present invention is to improve flexibility and transparency of a waterproof coating film in a fastener chain using a polyester resin material as the waterproof coating film. Another object of the present invention is to provide a slide fastener including such a fastener chain.

The present invention provides a slide fastener chain (fastener chain) having a structure in which fastener element rows of fastener elements, which are attached along respective side edge portions of a pair of fastener tapes each having a waterproof coating film formed on at least one main surface thereof, are engaged with each other on one side surface, wherein the waterproof coating film is formed from a polyester resin composition containing an aromatic polyester resin having one or two or more residues selected from the group consisting of an aliphatic dicarboxylic acid residue having 10 or more carbon atoms, an alicyclic dicarboxylic acid residue having 10 or more carbon atoms, 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 total content ratio of the aliphatic dicarboxylic acid residue having 10 or more carbon atoms, 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 in the total of all acid component residues and all diol component residues in the aromatic polyester resin is 0.5 to 8 mol%.

In another embodiment of the fastener chain 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 as a dimer acid residue.

In another embodiment of the fastener chain of the present invention, the aromatic polyester resin has at least one of the aliphatic diol residue having 10 or more carbon atoms and the alicyclic diol residue having 10 or more carbon atoms as a diol (dimerol) residue.

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

In another embodiment of the fastener chain of the present invention, the dimer alcohol residue is a hydrogenated dimer alcohol residue.

In another embodiment of the fastener chain of the present invention, the polyester resin composition contains polycarbodiimide.

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

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

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

In another embodiment of the fastener chain of the present invention, the fastener tape is made of polyester resin.

In another embodiment of the fastener chain of the present invention, the waterproof coating film enters into the irregularities of the main surface of the fastener tape at the interface with the fastener tape.

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

The present invention is a slide fastener provided with the slide fastener chain of the present invention on the other side.

The present invention is an article provided with the slide fastener of the present invention on the other side.

According to the fastener 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 base material of the fastener tape can be maintained even after the waterproof coating film is formed. Therefore, both waterproof property and aesthetic appearance can be achieved. In addition, when the waterproof coating film is dyed, the color tone can be easily adjusted to a desired color tone.

(2) Since the waterproof coating film of the present invention has excellent flexibility, the deterioration of the texture of the fastener tape and the deterioration of the slider slidability due to the formation of the waterproof coating film can be suppressed.

(3) When the fastener tape is made of a polyester resin material, the fastener tape and the waterproof coating film are made of the same resin, and therefore, a fastener chain having high recyclability and being environmentally friendly can be produced.

(4) The waterproof coating film of the present invention can also be directly formed on a fastener tape without using an adhesive. Thus, the working environment is improved, and special facilities and training are not required. In addition, the number of steps can be reduced and the manufacturing cost can be suppressed as compared with a method of attaching a waterproof film with an adhesive.

Drawings

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.

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

Fig. 4 shows an example of the configuration of an apparatus for forming a waterproof coating film on a fastener chain.

Fig. 5 shows a plan view and a side cross-sectional view (a-a view) of a test piece fixing jig used in the rain test B method.

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

Fig. 7 shows a state in which water that has passed through the test piece by sprinkling water is accumulated in the water storage member and accumulated.

Fig. 8 shows a state before the flexibility test apparatus is operated.

Fig. 9 shows a state in which the flexibility test apparatus is in operation.

[ description of reference numerals ]

10 zipper

11 tooth

12 slider

13 core wire

14 line

15 pulling sheet

16 top stop

18 zipper tape

19 Water-repellent coating film

21 zipper chain

22 polyester resin composition

23 mould

24 extruder

25 roll on the side of resin composition-coated surface

26 roll for non-coating surface side of resin composition

30 fixing clamp

32 water storage component

34 opening component

36 test sample

38-degree fixing tool

40 nozzle

42 piping

44 water quantity regulating valve

46 water accumulation

50 flexibility test device

51 moving member

52 load cell

53 pressure part

54 clamp

60 test sample

60a ring part

60b overlap portion

Detailed Description

(1. zipper chain)

Hereinafter, embodiments of the fastener chain according to the present invention will be described in detail with reference to the drawings. Fig. 1to 3 show an example of a slide fastener 10 provided with a fastener chain according to the present invention. Fig. 1 is a plan view of the entire slide fastener 10, fig. 2 is a sectional view showing a state where element rows of the fastener elements 11 are engaged with each other in the slider 12, and fig. 3 is a perspective sectional view of a part of the slide fastener 10.

An article in which the element rows of the elements are attached to the fastener tapes is referred to as a fastener stringer (fastener stringer). In addition, an article in which the fastener elements are coupled with each other by making each fastener stringer a pair is called a fastener chain. An article in which a slider, an upper stopper, a lower stopper, and the like are attached to a fastener chain is referred to as a slide fastener (fastener).

The fastener chain of the present invention has the following configuration in one embodiment: the fastener tape is formed by coupling fastener elements attached along respective side edge portions of a pair of fastener tapes each having a waterproof coating film formed on at least one main surface thereof with each other. Referring to fig. 2 and 3, the element row of the elements 11 is attached along one side edge of one main surface of each fastener tape 18. A slider 12 is inserted between the element rows of the right and left fastener elements 11, and the open/close state of the slide fastener 10 can be controlled by sliding the slider 12. As shown in fig. 1, the upper stopper 16 may be provided, and although not shown, a lower stopper, a separable bottom end stop, or the like may be attached. Preferably, one side edges of the pair of fastener tapes 18 are adjacent to each other at a predetermined interval (s is about 30 to 600 μm in fig. 2). The distance between the slider and the slider is set to improve the slidability of the slider 12. Although not limited, the fastener strips 18 are generally rectangular.

In the illustrated embodiment, the element rows of the linear nylon fastener element 11 having the core thread 13 inserted therein are sewn together by the sewing thread 14. Here, a double circular seam of a sewing machine is applied to the sewing thread 14. The element row of the nylon fastener element 11 may be formed of a monofilament of a synthetic resin such as polyamide or polyester, and is preferably made of a polyester resin from the viewpoint of improving the recyclability. The material of the slider 12, the stitches 14, and other members is also not particularly limited, but the recyclability can be further improved by making them of polyester resin.

(1-1. Water-repellent coating film)

In the illustrated embodiment, a waterproof coating film 19 made of a polyester resin composition is formed on the other main surface of each fastener tape 18. One of the features of the present invention is that the waterproof coating film 19 is formed of a polyester resin composition containing an aromatic polyester resin having one or two or more residues selected from the group consisting of an aliphatic dicarboxylic acid residue having 10 or more carbon atoms, an alicyclic dicarboxylic acid residue having 10 or more carbon atoms, an aliphatic diol residue having 10 or more carbon atoms, and an alicyclic diol residue having 10 or more carbon atoms (hereinafter, these residues may be collectively referred to as "residues having 10 or more carbon atoms"). This reduces the crystallinity of the polyester resin, and a waterproof coating film having excellent flexibility and transparency can be formed.

The polyester resin is a resin having a structure in which a dicarboxylic acid (in the present invention, the "dicarboxylic acid" includes an ester derivative thereof) and a diol component such as an aliphatic diol, an alicyclic diol, or an aromatic diol are connected to each other by an esterification reaction. One of the characteristics of the waterproof coating film according to the present invention is that an aromatic polyester resin is also used as the polyester resin. By using the aromatic polyester resin, such an advantage as excellent heat resistance can be obtained.

The aromatic polyester resin is 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 a plurality of at least one 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, one or more of an aromatic dicarboxylic acid residue and an aromatic diol residue and one or more of a residue having 10 or more carbon atoms are contained.

Examples of the dicarboxylic acid include aromatic dicarboxylic acids and aliphatic dicarboxylic acids, examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 1, 5-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, and 2, 6-naphthalenedicarboxylic acid, and examples of the aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Aromatic dicarboxylic acids are preferred for their excellent heat resistance. Examples of the ester derivative component include alkyl esters of these acids and acid halides. Examples of the aliphatic diol include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, 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 1, 4-dioxyethoxybenzene (1, 4-bisoxylethoxybenzene) and bisphenol A. Examples of the other diols include high molecular weight diols such as polyethylene glycol, polybutylene glycol, and polyhexamethylene glycol. These acid components and diol components may be used in combination.

The aromatic polyester resin having one or two or more residues having 10 or more carbon atoms can be produced as follows: the aromatic polyester resin is produced by copolymerizing one or more compounds 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 with other monomers constituting the aromatic polyester resin, as a monomer. In this case, the residue having 10 or more carbon atoms may be incorporated into the backbone of the polyester. The desired effect cannot be obtained only by simply mixing one or two or more compounds 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 with the polyester resin.

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 have preferably 20 or more carbon atoms, and more preferably 30 or more carbon atoms, because they are excellent in transparency. The upper limit of the carbon number is not particularly limited with respect to 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, but is preferably 54 or less, and more preferably 40 or less, from the viewpoint of solvent resistance and heat resistance.

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 either linear or branched, or saturated or unsaturated, but are preferably branched because of excellent flexibility and transparency, and are preferably saturated because of excellent colorless transparency.

The aliphatic dicarboxylic acid having 10 or more carbon atoms is not particularly limited, and examples thereof include linear and branched aliphatic saturated dicarboxylic acids such as sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, heptadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid, and linear and branched aliphatic unsaturated dicarboxylic acids such as decenedioic acid, undecenedioic acid, dodecenedioic acid, tridecanedioic acid, tetradecanedioic acid, heptadecenedioic acid, and hexadecanedioic acid.

The alicyclic dicarboxylic acid having 10 or more carbon atoms is not particularly limited, and examples thereof include compounds in which two functional groups represented by-A-COOH (in the formula, A represents a divalent saturated or unsaturated chain hydrocarbon group having 1 or 2 or more carbon atoms so that the carbon atoms of the entire compound are 10 or more) are bonded to a cycloalkane or cycloalkene. Examples of the cycloalkane include cyclohexane, cyclopentane, cycloheptane and the like. Examples of the cycloolefin include cyclohexene, cyclopentene, cycloheptene, and the like. More specific examples thereof include a cyclohexane ring having- (CH) bonded to the 1-and 4-positions, or to the 1-and 3-positions, respectively₂)_nA compound having a group represented by-COOH (n represents an integer of 1 or more), wherein- (CH) is bonded to each of the 1-and 3-positions of the cyclopentane ring₂)_n-COOH (n represents an integer of 1 or more) and- (CH)₂)_mA group represented by-COOH (m represents an integer of 2 or more).

Examples of the aliphatic diol having 10 or more carbon atoms include, but are not particularly limited to, straight-chain and branched-chain aliphatic saturated diols such as decanediol, undecanediol, dodecanediol, tridecanediol, tetradecanediol, pentadecanediol, hexadecanediol, heptadecanediol, octadecanediol, nonadecanediol, eicosanediol, heneicosanediol, docosanediol, tricosanediol, tetracosanediol, pentacosanediol, hexacosanediol, heptacosanediol, octacosanediol, nonacosanediol, triacontanediol, hentriacontanediol, and dotriacontanol, straight-chain and branched-chain aliphatic unsaturated diols such as decenediol, dodecenediol, tetradecenediol, hexadecenediol, and octadecenediol.

The alicyclic diol having 10 or more carbon atoms is not particularly limited, and examples thereof include compounds in which two functional groups represented by-B-OH (in the formula, B represents a divalent saturated or unsaturated chain hydrocarbon group having 1 or 2 or more carbon atoms so that the carbon atoms of the entire compound are 10 or more) are bonded to a cycloalkane or cycloalkene. Examples of the cycloalkane include cyclohexane, cyclopentane, cycloheptane and the like. Examples of the cycloolefin include cyclohexene, cyclopentene, cycloheptene, and the like. More specific examples thereof include a cyclohexane ring having- (CH) bonded to the 1-and 4-positions, or to the 1-and 3-positions, respectively₂)_nA compound having a group represented by-OH (n represents an integer of 2 or more), wherein- (CH) is bonded to each of the 1-and 3-positions of the cyclopentane ring₂)_n-OH (n represents an integer of 2 or more) and- (CH)₂)_mA compound having a group represented by-OH (m represents an integer of 3 or more).

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 as a dimer acid residue.

The "dimer acid" is a polycarboxylic acid obtained by polymerizing two or more molecules of unsaturated fatty acids through double bond portions. Dimer acid is mainly referred to as dimer, but also includes the concept of polymer such as trimer and tetramer. Even when a monomer of a monounsaturated fatty acid is used, copolymerization accompanying the esterification reaction does not proceed, and therefore, a skeleton of a polymer chain constituting the polyester cannot be formed, and a desired effect cannot be obtained. Dimer acid is available in the form of a mixture of two or more species, and is therefore often used in various applications as a mixture. Illustratively, the dimer acid can be obtained by dimerizing a linear or branched unsaturated fatty acid having 8 to 22 carbon atoms. In the present invention, a hydrogenated product of a dimer acid (hereinafter referred to as "hydrogenated dimer acid"), which is unsaturated or saturated dicarboxylic acid obtained by partially or completely hydrogenating unsaturated bonds of a dimer acid, is also included in the concept of a dimer acid. Hydrogenated dimer acid is preferred because it is superior in heat resistance and colorless transparency to dimer acid before hydrogenation.

The unsaturated fatty acid includes C8-22 fatty acids having 1-4 olefinic double bonds, and preferably C14-22 fatty acids having 1 or 2 olefinic double bonds.

Specific examples of the unsaturated fatty acid include octenoic acid, undecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecadienoic acid (linoleic acid, etc.), eicosadienoic acid, docosadienoic acid, octadecatrienoic acid (linolenic acid, etc.), eicosatetraenoic acid (arachidonic acid, etc.), tetradecenoic acid (crude rentzic acid), sperm whale acid, myristic acid), hexadecenoic acid (palmitoleic acid, etc.), octadecenoic acid (oleic acid, elaidic acid, vaccenic acid, etc.), eicosenoic acid (gadoleic acid, etc.), docosenoic acid (erucic acid, cetylenic acid, brassidic acid, etc.), etc. These may be used alone or in combination of two or more. Further, the dimer acid can be obtained by using, as a raw material, tall oil fatty acid, soybean oil fatty acid, palm oil fatty acid, rice bran oil fatty acid, linseed oil fatty acid, and the like, which are mixtures of unsaturated fatty acids.

The dimerization reaction is known, and for example, the reaction can be carried out at a high temperature of about 200 to 270 ℃ using a Lewis acid or a Bronsted acid type liquid or solid catalyst, preferably a smectite clay, as a catalyst. The dimer acid thus obtained is usually a mixture of dimer acids differing in structure depending on the bonding site of the double bond and isomerization, and may be used as it is, or may be used as a mixture. The dimer acid obtained may contain a small amount of a monomer acid (for example, 6% by mass or less, particularly 4% by mass or less), a polymer acid of a trimer acid or more (for example, 6% by mass or less, particularly 4% by mass or less), or the like.

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

[ solution 1]

In addition to the chain dimer acid represented by the structural formula (1), cyclic dimer acids represented by the following structural formulae (2) or (3), mixtures containing the same, and the like can also be obtained by dimerization reaction.

[ solution 2]

[ solution 3]

Examples of commercially available Dimer acids include HARIDIMER200, 300 (manufactured by HARIMACHEMICA L S GROUP), TSUNODIME 205, 395 (manufactured by Kunststoff industries Co., Ltd.), EMPO L (registered trademark) 1008, 1012, 1026, 1028, 1061, 1062 (manufactured by Cognis Co., Ltd.), and examples of hydrogenated Dimer acids include Dimer acid hydrogenated (manufactured by A L DRICH Co., Ltd.), PRIPO L (registered trademark) 1009 and the like (manufactured by Croda Co., Ltd.).

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

Typical examples of the diol include PRIPO L (registered trademark) 2033 (manufactured by Croda), KX-501 (manufactured by Mitsuwa chemical industry), Sovermol (registered trademark) 650NS (manufactured by BASF), and Sovermol918 (manufactured by BASF).

From the viewpoint of imparting excellent flexibility and transparency to the waterproof coating film, the total content ratio of the aliphatic dicarboxylic acid residue having 10 or more carbon atoms, 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 in the total of all acid component residues and all diol component residues in the aromatic polyester resin is preferably 0.5 mol% or more, more preferably 1 mol% or more, and still more preferably 2 mol% or more. The waterproof coating film has flexibility, and thus, the damage of the texture of the fastener tape and the deterioration of the slider slidability can be suppressed. The water-repellent coating film has transparency, so that the appearance of the fastener tape is not impaired as in the case of the conventional polyester water-repellent coating film.

However, when 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 deteriorated. Therefore, from the viewpoint of imparting excellent heat resistance to the waterproof coating film, the total content ratio of the aliphatic dicarboxylic acid residue having 10 or more carbon atoms, 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 in the total of all acid component residues and all diol component residues in the aromatic polyester resin is preferably 8 mol% or less, more preferably 5 mol% or less, and still more preferably 4 mol% or less.

To the polyester resin composition constituting the waterproof coating film, conventional additives such as dyes, pigments, heat stabilizers, weather resistant agents (ultraviolet absorbers and the like), hydrolysis resistant agents, antioxidants, lubricants and the like may be added as appropriate. The amount of each additive added is not limited, but is usually 10 parts by mass or less, for example, 0.1 to 5 parts by mass or 0.3 to 3 parts by mass, based on 100 parts by mass of the polyester resin. Even if an additive is added, the proportion 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, more typically 80% by mass or more, and may be 90% by mass or more, may be 95% by mass or more, and may be in the range of 80 to 99% by mass.

The polyester resin composition constituting the waterproof coating film may contain a hydrolysis-resistant agent, and the polyester resin composition of the present invention is particularly preferably a hydrolysis-resistant agent which is less likely to deteriorate in heat resistance because of its high flexibility. Among them, it is particularly preferable to add polycarbodiimide which is one of hydrolysis resistance agents, because it has excellent compatibility with polyester, hardly bleeds out in a high-temperature and high-humidity environment, hardly generates white turbidity, and is not easily volatilized at a high temperature of 200 ℃. The amount of the polycarbodiimide to be added is not limited, and when the amount is too large, the heat resistance tends to be lowered, whereas when the amount is too small, the effect of improving the hydrolysis resistance tends to be hardly obtained, and therefore, the amount is usually 10 parts by mass or less, for example, 0.1 to 5 parts by mass or 0.3 to 3 parts by mass based on 100 parts by mass of the polyester resin.

The polycarbodiimide is a compound having a structure represented by (-N ═ C ═ N —), i.e., a carbodiimide group, and can be produced, for example, by heating an organic isocyanate in the presence of an appropriate catalyst and subjecting the heated isocyanate to a decarboxylation reaction. Preferably, polycarbodiimide having a number average molecular weight of 8000 or more is used. The number average molecular weight of the polycarbodiimide may be obtained as follows: polycarbodiimide powder was dissolved in a single solvent or a mixed solvent of two or more selected from chloroform, Tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), and Hexafluoroisopropanol (HFIP), and the number average molecular weight obtained based on polystyrene standards was measured by measuring the curve (curve) of the molecular weight distribution curve using GPC.

When the number average molecular weight of the polycarbodiimide is less than 8000, the volatility increases, and thus the degree of decrease in the reaction rate constant decreases. 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 is preferably 30000 or less from the viewpoint of mobility of the polymer chain. The number average molecular weight of the polycarbodiimide is preferably 8000 to 30000, more preferably 8000 to 15000, from the viewpoint of volatility and mobility of the polymer chain.

The polycarbodiimide may be selected from compounds obtained by polymerizing aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, or a mixture thereof, examples of the polycarbodiimide include poly (1, 6-hexamethylene carbodiimide), poly (4,4 ' -methylenedicyclohexylcarbodiimide), poly (1, 3-cyclohexylenedicarbodiimide), poly (1, 4-cyclohexylenedicarbodiimide), poly (4,4 ' -dicyclohexylmethane carbodiimide), poly (4,4 ' -diphenylmethane carbodiimide), poly (3,3 ' -dimethyl-4, 4 ' -diphenylmethane carbodiimide), poly (naphthylenedicarbodiimide), poly (P-phenylenedicarbodiimide), poly (m-phenylenedicarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimides), poly (methyl-diisopropylphenylenedicarbodiimide), poly (1, 3-triisopropylphenylenedicarbodiimide), poly (1-2-110-2000-2-2000-2-2000-and the like.

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 or the like, and thus the adhesiveness tends to be relatively high. Therefore, in order to improve the slidability between the slider and the waterproof coating film, it is also preferable to add a lubricant to the polyester resin composition constituting the waterproof coating film in order to lower the adhesiveness of the polyester resin composition to facilitate blending at the time of composite production, and further in order to make the fastener stringers coated with the waterproof coating film less likely to adhere to each other. The amount of the lubricant to be added is not limited, and if the amount is too large, bleeding may occur, whereas if the amount is too small, the desired effect is difficult to obtain, and therefore, the amount is usually 10 parts by mass or less, for example, 0.1 to 5 parts by mass or 0.3 to 3 parts by mass, based on 100 parts by mass of the polyester resin.

Examples of the lubricant include synthetic resin-based lubricants (fluorine-based resins, acrylic resins, and the like), paraffin-based lubricants (natural paraffin, synthetic paraffin, and the like), higher fatty acid-based lubricants (stearic acid, montanic acid, and the like), ester-based lubricants (fatty acid esters, aromatic esters, and the like), fatty acid amide-based lubricants (erucamide, stearic acid amide, and the like), and the like. These lubricants may be used alone or in combination of two or more. Among these, a fatty acid amide-based lubricant is preferable because of its excellent sliding properties.

In addition, in order to prevent yellowing due to sunlight, it is also particularly preferable to add an ultraviolet absorber to the polyester resin composition constituting the water-repellent coating film. The ultraviolet absorber is not limited, and examples thereof include indole-based, triazine-based, benzotriazole-based, benzophenone-based, benzoate-based, cyanoacrylate-based, and salicylate-based ones, and one kind thereof may be used alone, or two or more kinds thereof may be used in combination. Among these, benzotriazole-based ultraviolet absorbers are preferred because of their excellent stability under high temperature and high humidity conditions and their low coloration due to addition.

In addition, a pigment having a hiding power (light scattering property) may be added as the ultraviolet absorber. Although not particularly limited, inorganic white pigments such as titanium oxide, inorganic pigments having reflection characteristics, black pigments such as carbon black, and the like can be preferably used in view of particularly excellent color tone and hiding power (light scattering property). It is preferable to add a pigment having the same color as that of the fastener tape, since a zipper having a high quality appearance can be formed. In particular, it is preferable to add red, blue or yellow pigments to the inorganic white pigment and to add a pigment having the same color as that of the fastener chain.

Examples of the inorganic white pigment include ZnO and TiO₂、Al₂O₃·nH₂O、[ZnS+BaSO₄]、CaSO₄·2H₂O、BaSO₄、CaCO₃、2PbCO₃·Pb(OH)₂And the like. Among the inorganic white pigments, titanium oxide (TiO)₂) Since the color tone and the hiding power (light scattering property) are particularly excellent, the color tone and the reflection of the white resin film can be facilitatedThe improvement of the radiation characteristics is preferable. Titanium oxide in two crystal forms of anatase type and rutile type is widely used. In the present invention, these two crystal forms of titanium oxide can be used, and among them, titanium oxide having a rutile type crystal form is preferable from the viewpoint of excellent dispersibility in an aromatic polyester resin and extremely low volatility.

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 based on a transmission electron microscope image is usually in the range of 150 to 1000nm, preferably 200 to 700nm, and more preferably 200 to 400 nm. When the average particle diameter of titanium oxide is too small, the hiding power is lowered. When the average particle diameter of titanium oxide is within the above range, the refractive index is high and the light scattering property is strong, so that the hiding power as a white pigment is high. Titanium oxide generally exists in the form of secondary particles after primary particles are aggregated. The specific surface area of titanium oxide obtained by the BET method is usually 1to 15m²(ii)/g, in most cases, 5 to 15m²In the range of/g.

As the black pigment, carbon black is preferable. The carbon black is not particularly limited, and furnace black, chimney black (channel black), acetylene black, thermal black (thermal black), and the like may be used, and carbon black having a surface modified with a carboxyl group or the like may be used. The average particle diameter (average primary particle diameter) of the carbon black obtained by image analysis based on a transmission electron microscope image is usually in the range of 10 to 150nm, preferably 13 to 100nm, and more preferably 15 to 40 nm. If the average particle diameter of the carbon black is too small, aggregation is likely to occur, which may make handling difficult. If the average particle size is too large, dispersion failure and appearance failure may occur. The specific surface area of the carbon black based on the BET method is usually 20 to 250m²A concentration of 50 to 200m²(ii) g, more preferably 80 to 200m²In the range of/g.

The amount of the ultraviolet absorber added is not limited, and if the amount is too large, bleeding tends to occur, whereas if the amount is too small, the desired effect is difficult to obtain, and therefore, the amount is usually 10 parts by mass or less, for example, 0.1 to 5 parts by mass, or 0.3 to 3 parts by mass, based on 100 parts by mass of the polyester resin.

The waterproof coating film of the present invention is composed of a polyester resin composition, and therefore can be easily dyed, and can be colored in various colors by inkjet dyeing, for example. Further, the waterproof coating film of the present invention is high in transparency, and therefore, the color tone can be easily controlled by coloring.

In order to enable extrusion from a die and curtain coating (curing), the polyester resin composition used for the water-repellent coating film desirably has a melt viscosity at 200 ℃ in the range of 50 to 3000dPa · s. By setting the melt viscosity at 200 ℃ to 50 dPas or more, preferably 100 dPas or more, more preferably 200 dPas or more, it is possible to prevent the flow rate of the molten resin from becoming too high and going out of the range of the fastener tape, and to improve the film thickness controllability. Further, when the melt viscosity at 200 ℃ is set to 3000dPa · s or less, preferably 2000dPa · s or less, more preferably 1000dPa · s or less, the flow rate can be prevented from becoming too small and the coating film forming speed can be prevented from being lowered, the load on the extruder or the die can be prevented from increasing, and the extrusion of the resin to the fastener tape during curtain coating can be suppressed.

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. When the number of branched structures in the constituent components is increased, the melt viscosity is decreased, and when the number of long-chain structures is increased, the melt viscosity is increased.

In the present invention, the melt viscosity is measured by the following method. The sample was preheated at 200 ℃ for 15 minutes, and then measured by reading the value of the viscosity at 200 ℃ with a B-type viscometer in accordance with JIS K7117-1 (1999).

Referring again to fig. 1to 3, the waterproof coating film 19 extends in the longitudinal direction and the width direction of the fastener tape 18 so as to cover the entire main surface. In the illustrated embodiment, the outer surface of the waterproof coating film 19 is at least flat at a predetermined portion thereof through which the slider 12 passes. This is to smooth the sliding of the slider 12. The outer surface of the waterproof coating film 19 at a portion where the slider 12 does not pass may have a concave-convex shape, but from the viewpoint of ease of production and good appearance, it is preferable that the entire outer surface of the waterproof coating film 19 is flat.

In order to effectively exhibit the waterproof function, it is preferable that the side on which the waterproof coating film 19 is formed is an outer side and the element row of the fastener element 11 is an inner side and is attached to the article. From the viewpoint of ease of opening and closing operation, the pull tab 15 of the slider 12 is preferably attached to the outside.

In the illustrated embodiment, in a state where the fastener chain is closed, the end edges of the waterproof coating film 19 formed on the main surface of each fastener tape 18 extend from the one side edge of each fastener tape 18 in a direction approaching each other and abut against each other. This ensures waterproofness. The edges of the waterproof coating film 19 abut against each other near the coupling center line a of the element row of the element 11, and the slider 12 can slide smoothly.

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 improving abrasion resistance and scratch strength. The thickness of the waterproof coating film 19 is preferably 350 μm or less, more preferably 300 μm or less, and still more preferably 200 μm or less, from the viewpoint of preventing the lowering of flexibility of the fastener tape and the occurrence of dents on the outer surface due to impact.

In the present invention, the thickness of the waterproof coating film 19 is measured by the following method. First, 16 samples each having a square shape with a side length of 5mm were cut out from a fastener chain at intervals of 20mm or more in the longitudinal direction and at intervals of 5mm or more in the width direction. The cut sample was imaged by using a microfocus X-ray fluoroscopy/CT apparatus (for example, "SMX 225 CT" manufactured by Shimadzu corporation). Measurement conditions of the microfocus X-ray fluoroscopy/CT apparatus are shown below.

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

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

VOXEL SIZE：0.012mm

Voltage of X-ray tube: 90kV

Current of the X-ray tube: 40 muA

Number of views (number of views): 1200

Average number: 10

Slice thickness: 0.013mm

Image size 512 × 512pixel

A microfocus X-ray fluoroscopy/CT apparatus includes: an X-ray tube for emitting X-rays, an X-ray detector for detecting X-rays, and a rotary table on which an object to be measured is placed and rotated. From the CT image obtained by imaging, 3 sites of the thickness of the waterproof coating film were measured at 1mm intervals in the longitudinal direction of the fastener chain, and the average value was calculated. This measurement was performed on the cut 16 samples, and the average value of 16 samples was taken as the measured value of the thickness of the waterproof coating film.

(1-2. zipper tape)

The material of each fastener tape 18 is not particularly limited, and may be natural fibers or synthetic fibers generally used for fastener tapes, and examples thereof include polyamide resin fibers, polyester resin fibers, and acrylic resin fibers. The fastener tape can be produced by weaving or knitting these synthetic fibers. In terms of improving recyclability, polyester resin fibers are preferably used.

As the polyester resin for the fastener tape, any known polyester resin can be used as the polyester resin for the fastener tape, and as the polyester resin for the fastener tape, an aromatic polyester resin is also preferable. Specific examples of the polyester resin for the fastener tape include polyester resins selected from polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and a combination thereof. Among them, polyethylene terephthalate (PET) resins are preferred because of their excellent mechanical strength and dyeability. The polyester resin may be appropriately added with conventional additives such as dyes, pigments, heat stabilizers, weather stabilizers, hydrolysis stabilizers, antioxidants, and the like.

More than one of the core thread, the fastener element and the fastener tape may be subjected to waterproof processing. As a method of water repellent treatment, a method of adhering a water repellent to the surface of an object member is exemplified. For the fastener tape, a water repellent can be attached to the above water repellent coating film.

As the water repellent, a fluorine-based compound, an organosilicon-based compound, an acrylic-based water repellent, a silicon composite-based (silicone composite) water repellent, a paraffin-based compound, an ethylene urea-based compound, a zirconium-based compound, a fatty acid amide-based compound, a methylolamide-based compound, an alkyl urea-based compound, a fatty acid amide-based compound, or the like can be used.

Examples of the water repellent agent for the fluorine-based compound include pentadecafluorooctyl polyacrylate, trifluoroethyl polyacrylate, tetrafluoroethylene-hexafluoropropylene copolymer, perfluorolauric acid, polytetrafluoroethylene, perfluoro-n-alkylacrylate, polyvinylidene fluoride, pentadecanobutylethyl methacrylate, and hexafluoropropylene.

As the water repellent for other fluorine-based compounds, a copolymer of two or more kinds of fluorine atom-containing olefins, a copolymer of a fluorine atom-containing olefin and a hydrocarbon monomer, or the like can be used. In addition, in order to improve the durability of the water repellency, it is preferable that a water repellent be added to the fabric together with the binder resin.

As the silicon-based compound, there can be used: silicone-based water repellent agents comprising various modified silicones such as polydimethylsiloxane, methylhydrogenpolysiloxane, amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, quaternary ammonium salt-modified silicone, higher alkyl-modified silicone and fluorine-modified silicone, and a curing accelerating catalyst such as methylhydrogenpolysiloxane and an aromatic curing accelerating catalyst such as toluene, xylene, n-hexane and n-heptane. The organosilicon waterproofing agent has the following advantages: (1) a large contact angle with water and excellent water repellency; (2) the surface tension is small, so that the substrate is easy to wet, and a uniform film can be formed; (3) has air permeability; (4) excellent durability, excellent washing resistance and dry-cleaning resistance, and the like.

Further, as the silicone-based water repellent, there can be used: a silicone emulsion comprising an anionically stabilized hydroxyl group-containing diorganopolysiloxane, colloidal silica, and a curing catalyst, as described in Japanese patent application laid-open Nos. 58-118853 and 60-96650; or a room-temperature-curable aqueous silicone emulsion composition which is cured at room temperature by removing moisture and provides an elastomeric cured product, such as a silicone emulsion comprising an ionically or nonionically stabilized alkoxy group-containing diorganopolysiloxane and a titanium catalyst, as described in Japanese patent application laid-open No. 7-150045.

In addition, in order to improve the durability of the water repellent, a crosslinking agent may be used in combination with the above compounds. As the crosslinking agent, melamine-based resins, blocked isocyanate-based resins, imine-based resins, and the like can be used.

In addition, a binder resin may be contained together with the above compound in order to improve the durability of the water repellent. As the binder resin, acrylic resin, urethane resin, silicone resin, or the like can be used.

The crosslinking agent and the binder resin may be used in combination, and in this case, the treatment liquid may be used in the form of a mixed solution of the polyfluoroalkyl group-containing acrylic copolymer and the aminoplast resin or the polyfunctional blocked isocyanate-containing urethane resin.

(2. method for manufacturing slide fastener chain)

Next, an example of the method for manufacturing a fastener chain according to the present invention will be described with reference to fig. 4. First, a fastener chain 21 is prepared, the fastener chain 21 including a pair of fastener tapes having one side edge adjoining to each other at a predetermined interval, and a fastener element row attached to a main surface of the one side edge of each fastener tape. The description of the members constituting the fastener chain 21 is as described above.

Next, the polyester resin composition 22 having a melt viscosity at 200 ℃ in the aforementioned range is extruded at 150 to 250 ℃ at the outlet of the die 23, and the polyester resin composition 22 is curtain-coated on the main surface which is the main surface of each fastener tape and is on the opposite side to the main surface on which the element rows are mounted and the aforementioned interval(s). The extrusion of the polyester resin composition can be carried out by a conventional extrusion molding method using an extruder 24 and a die 23, for example. The reason for setting the melt viscosity at 200 ℃ of the polyester resin composition 22 is as described above. The reason why the temperature of the polyester resin composition 22 at the outlet of the die 23 is set to 150 ℃ or higher is to make the resin composition have a coatable viscosity. The temperature of the polyester resin composition at the die outlet is preferably 170 ℃ or higher, more preferably 190 ℃ or higher. The reason why the temperature of the polyester resin composition at the die outlet is set to 250 ℃ or lower is to prevent thermal deterioration of the resin composition. The temperature of the polyester resin composition at the die outlet is preferably 230 ℃ or less, more preferably 210 ℃ or less.

The polyester resin composition is preferably coated on the main surface of the fastener tape by curtain coating. Since the polyester resin composition immediately after being discharged from the die exit is at a high temperature and has a relatively high fluidity, the polyester resin composition is likely to enter a gap formed by a space(s) provided between a pair of fastener tapes when the polyester resin composition is pressed into the fastener tapes under a high pressure. If the polyester resin composition excessively enters the gap, the polyester resin composition comes into contact with the slider, and the waterproof coating film may be damaged by sliding of the slider.

In this regard, in the case of curtain coating, the pressure of the molten polyester resin composition discharged from the die outlet at the time of discharge is released into the air and then reaches the main surface of the fastener tape, and therefore, the extrusion of the main surface of the fastener tape from the polyester resin composition can be made small. Thereby, the polyester resin composition can be prevented from entering into a gap generated by the gap(s) provided between the pair of fastener tapes to an inappropriate degree.

Further, by curtain coating a polyester resin composition having a predetermined melt viscosity, the polyester resin composition of a desired shape and size can be laminated on the fastener tape. Therefore, depending on the shape and size of the die outlet, the coating can be applied in a desired thickness and width, or in a band-like shape with a uniform thickness. It is advantageous in industrial production to carry out curtain coating while conveying the fastener chain in the longitudinal direction thereof.

The die exit preferably extends across the entire width of the pair of fastener tapes. Thereby, a waterproof coating film can be formed on the main surfaces of the pair of fastener tapes without interruption in the tape width direction. In addition, the thickness of the polyester resin composition coated on the fastener tape can be controlled by adjusting the slit width (w) of the die outlet. From the viewpoint of maintaining the strength of the resin layer, the slit width (w) is preferably 0.01mm or more, more preferably 0.05mm or more, and still more preferably 0.1mm or more. In order to prevent an increase in weight and a decrease in flexibility due to an increase in the thickness of the resin layer, the slit width (w) is preferably 0.8mm or less, more preferably 0.4mm or less, and still more preferably 0.25mm or less.

The curtain coating can set the pressure of the polyester resin composition discharged from the die outlet to the main surface of the fastener tape to 1MPa or less, and if the pressure is in this range, the penetration of the polyester resin composition into the gap between the pair of fastener tapes can be effectively suppressed. The pressure is preferably 0.8MPa or less, more preferably 0.5MPa or less. However, if the pressure of the polyester resin composition discharged from the die outlet to the fastener tape main surface is too small, the resin does not enter between fibers of the fastener tape and the adhesion is reduced, and therefore the pressure is preferably 0.1MPa or more, more preferably 0.2MPa or more.

In the present invention, the pressure can be measured as follows: the pressure applied to the fastener tape was measured by providing a pressure gauge below the fastener tape and continuously flowing the polyester resin composition.

As shown in FIG. 4, the pressure of the polyester resin composition discharged from the die outlet against the main surface of the fastener tape can be controlled by adjusting the distance (g) from the die outlet to the main surface of the fastener tape where the polyester resin is curtain-coated, and the distance (g) can be set to 0.1 to 2.0mm, for example. From the viewpoint of preventing the mold from coming into contact with the fastener tape having the surface irregularities, the distance (g) is preferably 0.1mm or more, more preferably 0.3mm or more, and still more preferably 0.5mm or more. From the viewpoint of maintaining the shape of the die from the exit, the distance (g) is preferably 2.0mm or less, more preferably 1.5mm or less, and still more preferably 1.0mm or less.

As shown in FIG. 4, after curtain coating a polyester resin composition 22 on the main surface of a fastener tape, the fastener tape is passed through a metal roller 25 heated to 100 to 250 ℃ from the side of the polyester resin composition coated surface and a roller 26 having a hardness of 5 to 50 DEG from the side of the polyester resin non-coated surface (fastener tape) while applying a pressure of 0.1 to 10.0MPa to the fastener chain 21. Through this process, the polyester resin moderately enters fine irregularities on the main surface of the fastener tape, and the adhesive strength is improved based on the anchor effect. This process is carried out continuously while conveying the fastener chain in the longitudinal direction thereof after curtain coating, and is advantageous in industrial production.

The metal roller 25 is used on the side of the polyester resin composition coated surface for the following reasons: the polyester resin composition applied to the fastener tape is excellent in mechanical strength, heat resistance and smoothness, and is difficult to adhere to a roller. By heating the roller 25 to 100 to 250 ℃, the polyester resin composition is softened and further enters the fine unevenness of the fastener tape, and a more firm anchoring effect can be obtained. The heating temperature of the roller 25 is preferably 120 ℃ or higher, more preferably 150 ℃ or higher, for the reason of promoting softening of the polyester resin composition. From the viewpoint of preventing thermal deterioration of the polyester resin composition, the heating temperature of the roller 25 is preferably 220 ℃ or lower, and more preferably 200 ℃ or lower.

By using a soft roller 26 having a hardness of 5 to 50 ° on the non-coated surface (fastener tape) side of the polyester resin composition, the surface of the roller deforms following the fine irregularities on the main surface of the fastener tape when the fastener chain passes through the roller, and therefore, the adhesion of the polyester resin to the fastener tape is further promoted, and the defective adhesion portion can be reduced. The reason why the hardness of the roller is set to 5 ° or more is as follows: the plastic deformation due to the excessive softness of the roller is prevented, and is preferably 7 ° or more, and more preferably 10 ° or more. The reason why the hardness of the roller is set to 50 ° or less is as follows: the roller is prevented from becoming too hard and hindering the fine uneven follow-up, and is preferably 40 ° or less, and more preferably 30 ° or less. The material having the hardness in the above range is not limited, and silicone resin, polytetrafluoroethylene resin, rubber roll, and the like can be mentioned, and silicone resin is preferable for the reason that flexibility is maintained for a long time.

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

It is not necessary to heat the roller 26 on the non-coated side (fastener tape) side of the polyester resin composition. If the roller on the fastener tape side is heated, the tape is directly heated because resin is not applied, and this is in view of the possibility of thermal deformation of the fastener tape itself.

The pressure at which the fastener chain coated with the polyester resin composition is passed between the rolls is preferably 0.5MPa or more, more preferably 1.0MPa or more, and still more preferably 1.5MPa or more, from the viewpoint of reliably bringing the rolls into close contact with the resin composition-coated surface. From the viewpoint of preventing leakage of the resin layer due to an excessive pressure, the pressure is preferably 10MPa or less, more preferably 5MPa or less, and still more preferably 2MPa or less.

In the present invention, the pressure at the time of roller passage is measured as follows: the pressure at which the non-coated side roller of the resin composition was pressed against the coated side roller of the resin composition was measured by a bourdon tube pressure gauge according to JIS B7505(1999) with the fastener tape sandwiched between the rollers.

Next, by cooling and solidifying the aforementioned polyester resin on the fastener chain, the waterproof coating film is firmly fixed on the main surface of the fastener tape. As the cooling condition, air may be blown to the belt surface for cooling. In the case of rapidly cooling the resin, excessive deformation due to shrinkage occurs, and therefore, for the purpose of preventing the occurrence of the excessive deformation, the wind speed at this time is preferably 30m/s or less, more preferably 20m/s or less, and still more preferably 10m/s or less. This cooling process is also industrially advantageous in that the fastener chain is continuously carried out with its lengthwise conveying side after the roller pressing.

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 aforementioned space(s) of the fastener chain is cut between the spaces. Preferably along the centerline a of the space. For example, the sheet may be cut by a slitter (not shown). This cutting step is also industrially advantageous in that the fastener chain is continuously conveyed in its longitudinal direction while being cut.

The slide fastener of the present invention can be suitably used as opening and closing tools for daily necessities such as clothing, bags, footwear, and miscellaneous goods, as well as protective clothing such as space suits, chemical protective clothing, diving suits, lifeboats, and life jackets, covers for transport containers, tents, and the like.

Examples

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

< test example 1 >

(1. preparation of polyester resin)

In a 2-liter three-necked flask equipped with a stirrer, a condenser and a thermometer, the following components were charged in respective proportions corresponding to the respective test numbers shown in Table 1 (tables 1to 1 and 1to 2): terephthalic acid (TPA), isophthalic acid (IPA), Dimer Acid (DA), Adipic Acid (AA), Sebacic Acid (SA), hydrogenated dimer acid (H-DA), 1, 6-naphthalenedicarboxylic acid (NDCA), and 1, 12-dodecanedioic acid (DDA) as dicarboxylic acids; ethylene Glycol (EG), 1, 2-Propanediol (PG), 1, 4-butanediol (1,4-BG), diethylene glycol (DEG), 1, 4-Cyclohexanedimethanol (CHDM), 1, 12-Dodecanediol (DMG), 4-hydroxymethylcyclohexanepropanol (HCHP), 4-hydroxymethylcyclohexanoisopropanol (HCHIP), dimer alcohol (DG), and hydrogenated diol (H-DG) as diols; and a small amount of tetraisopropyl titanate as a catalyst, and the temperature was raised to 180 ℃ while stirring, and then gradually raised from 180 ℃ to 240 ℃ while stirring, and the esterification reaction was carried out at 240 ℃ under normal pressure for 5 hours. Then, the pressure in the flask was gradually decreased to 133Pa (1torr), and the reaction was carried out for 5 hours after reaching 133Pa, thereby obtaining highly viscous syrup-like polyester resins (P-1 to P-27) having various resin compositions shown in Table 1.

The Dimer Acid (DA), hydrogenated dimer acid (H-DA), Diol (DG) and hydrogenated diol (H-DG) used herein are as follows:

HARIDIMER200 (manufactured by HARIMA CHEMICA L S GROUP, carbon number of main component 36) Dimer Acid (DA): HARIDIMER

Hydrogenated dimer acid (H-DA) PRIPO L1009 (C36, Croda corporation, main component)

Diol (DG): HARIDIMER200 reduced product of carboxyl group

Hydrogenated diol (H-DG) which is a reduction of the carboxyl group of PRIPO L1009

(2. preparation of a Compound of polyester resin composition)

The synthetic polyester resin has rubber elasticity and cannot be pulverized by a pulverizer at normal temperature, and therefore, the synthetic polyester resin is mixed with dry ice, and then put into a pulverizer to be frozen and pulverized, followed by drying, thereby producing a polyester resin powder. Then, with respect to 100 parts by mass of the polyester resin shown in table 2, the following components were added in terms of polycarbodiimide: 0.5 part by mass of an ultraviolet absorber: 0.5 parts by mass of a lubricant: 1.0 part by mass was dry-blended in a mixer to prepare a polyester resin composition composite. The additives used are as follows.

Polycarbodiimide manufactured by Rhein Chemie, trade name "STABAXO L P-100" (hereinafter referred to as "P-100")

Lubricant: manufactured by Kao corporation, trade name "fatty acid amide S" (hereinafter referred to as "amide S")

Ultraviolet absorber (benzotriazole series): CHEMICRO KASEI Corporation under the trade name "KEMISORB 73" (hereinafter referred to as "KEMISORB 73")

(3. production of slide fastener chain)

In each test example, 2 long polyester resin fastener tapes each having a tape width of 16.5mm and a tape thickness of 0.6mm were prepared, a nylon element row made of polyester resin was sewn to a side edge of each fastener tape, and opposing element rows were engaged with each other to assemble a fastener chain.

(4. production of slide fastener chain: formation of Water-repellent coating film by curtain coating)

The polyester resin composition composite prepared above was put into a curtain coating apparatus having a structure shown in fig. 4, and the polyester resin composition (waterproof coating film) was continuously coated on white and black fastener chains conveyed in the longitudinal direction. At this time, the conveying speed of the fastener chain was set to 10m/min, the temperature of the die exit was set to 200 ℃ (the melt viscosity of each resin composition at 200 ℃ was about 500 to 800dPa · s), and the slit width (w) of the die exit was set to 33 mm. Further, the distance (g) from the die outlet to the main surface of the fastener tape was 1.0mm, the discharge amount of the polyester resin composition was 250g/min, and the pressure of the resin composition against the main surface of the fastener tape during curtain coating was 0.4 MPa. After the coating, air was blown to the surface of the fastener tape at a wind speed of 10m/s, thereby cooling and solidifying the polyester resin composition. Finally, a fluorine-based water-soluble water repellent agent was applied to the surface of the fastener tape opposite to the surface coated with the water repellent coating film, including the surface of the nylon fastener element rows, by a roll coater and dried to obtain white and black fastener chains (F-1 to F-28) having a water repellent coating film thickness of about 120 to 140 μm.

[ tables 1-1]

[ tables 1-2]

[ Table 2]

(5. evaluation of characteristics of slide fastener chain)

Various characteristics of each of the fastener chains obtained as described above were evaluated.

(1) Flexibility test

Fig. 8 shows a state before the flexibility test apparatus 50 is operated. Fig. 9 shows a state in which the flexibility test device 50 is operated to press the fastener chain. A test specimen 60 of a fastener chain of 120mm or more was bent into a loop shape near the center so that the elements were engaged and the nylon elements were positioned inside, thereby forming a loop portion 60a and overlapping portions 60b at both ends. The length of the ring portion 60a is set to 80mm, and the length of the overlapping portion 60b is set to 20mm or more. The overlapping portion 60b is preferably fixed with tape or the like.

As shown in fig. 8, the flexibility test apparatus 50 used in the flexibility test includes: a moving member 51 that moves up and down; a load sensor 52 attached to the moving member 51 and converting a load into an electric signal; a pressurizing unit 53 attached to the load cell 52 and pressurizing a ring portion 60a of the test sample 60; and a clip 54 that fixes the overlapping portion 60b of the test specimen 60.

The clip 54 supports the test specimen 60 in a state where the loop portion 60a protrudes upward and the overlapping portion 60b is sandwiched. In this state, the moving member 51 moves downward. When the moving member 51 moves downward, the load sensor 52 and the pressurizing unit 53 also move downward. Then, as shown in fig. 9, the pressing portion 53 presses the ring portion 60 a. After the tester moves the moving member 51 downward to a predetermined position, the maximum load in the moving range is checked by the load sensor 52. For each test sample, 5 tests were carried out, and the average value was determined.

(2) Reciprocating opening and closing test

A reciprocating opening and closing durability test with 500 times of opening and closing was performed on MH scale according to JIS S3015 (2007). The sample after the test was subjected to the passing position of the slider on the surface of the waterproof coating film (observation area 750 mm) according to the following criteria²) The appearance of (4) was evaluated. The evaluation criteria are as follows.

◎ No scratches or sliding marks were observed at all.

○ slight scratches, sliding marks were observed.

△ scratches, sliding marks were observed.

× film peeling was observed.

Note that △ or more is an acceptable level as a product.

(3) Transparency of

The black fastener chain was visually evaluated for transparency immediately after production and after one week at room temperature, as described below, and the color range of the black fastener chain before application of the water-repellent coating film was L^*a^*b^*(D65) Is numbered as L^*＝19.0～21.0、a^*＝-1.0～1.0、b^*＝-1.0～1.0。

◎, transparency and no whitening at all.

○, partial slight whitening was confirmed.

△, slight whitening was observed as a whole, but no practical problem was found.

×, significant whitening was observed, which caused practical problems.

(4) Colorability

For white zipper chain, b of white zipper chain before waterproof coating film is coated^*As a reference, the color difference Δ b was measured^*The color range of the white fastener chain before coating with the polyester resin was L^*a^*b^*(D65) Is numbered as L^*＝88.0～90.0、a^*＝-1.0～1.0、b^*Color measurement was performed using a spectrocolorimeter CM-3700A manufactured by KONICA MINO L TA, reflection measurement of SCI with a diameter of 5 × 7mm, and measurement of 15 points at 1CM intervals was performed by cutting out tape portions of the fastener chain, and the color difference Δ b was measured^*The average value of (A) is classified as the coloring property in the following grades.

◎ less than 2.0

○ is more than 2.0 and less than 3.0

△ is 3.0 or more and less than 4.0

× ratio of more than 4.0

If the average molecular weight is less than 4.0, the level is practically no problem.

(5) Water resistance test

A water repellency test was performed according to the rain test B method (see JIS L1092 (2009) appendix JA), a description will be given of a fixing jig for a sample of a produced fastener chain with reference to fig. 5, and fig. 5 is a view showing a plan view and a side cross-sectional view (a-a view) of the fixing jig for a test sample used in the rain test B method.

As shown in fig. 5, the fixing jig 30 includes: an opening member 34 having an opening window for allowing water descending from above to contact a test sample 36; and a water storage member 32 disposed below the opening member 34 and having a retention portion for retaining moisture penetrating the test specimen 36. The test sample 36 is used while being sandwiched between the opening member 34 and the water storage member 32. In addition, in the rain test B method, the fixing jig 30 is fixed at an angle of 45 degrees by using the angle fixing tool 38 so as to maintain a predetermined inclination without submerging the test specimen 36 in water, and a rain test is performed. As shown in fig. 5, the opening window of the opening member 34 has a window length of 200mm and a window width of 15 mm. In addition, the length of the test sample 36 was 250 mm.

Fig. 6 is a view showing an external appearance of an artificial rainfall device when the rain test B method is performed. The fixing jig 30 and the angle fixing jig 38 are shown in cross section. As shown in fig. 6, the fixing jig 30 with the test specimen 36 mounted thereon is placed on the angle fixing jig 38 and set at an angle of 45 degrees. A nozzle 40 for spraying water was disposed at a position 2000mm above the fixing jig 30. A water supply pipe 42 is connected to the nozzle 40 to supply water under pressure to the inside. A water amount adjusting valve 44 for adjusting the amount of water to be sprayed is disposed in the middle of the pipe 42.

In the case of the rain test B method, the test specimen 36 is cut into a length of 250mm, and the mass (M) before the test is measured in advance₀). Then, the test specimen 36 is held at a predetermined position between the opening member 34 and the water storage member 32. At the same time, a suction paper for sucking the water accumulated in the water storage member 32 after the end of the test to measure the mass of the water passing through the test sample 36 is prepared, and the initial mass (M) of the suction paper is measured in advance₁)。

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

After the water application is completed, the test specimen 36 is first removed from the fixing jig 30, and the mass (M) of the test specimen 36 after the test is measured₂). The absorbent paper is immersed in the accumulated water 46 (see fig. 7) accumulated in the water storage member 32, and absorbs all of the water accumulated in the water storage member 32. Then, the mass (M) after water absorption was measured₃)。

Then, the amount of penetration (g) is calculated as (M)₂-M₀)+(M₃-M₁) The amount of water permeated by the rain test method B was calculated.

Fig. 7 shows a state in which water having permeated the test sample 36 by spraying water is accumulated in the water storage member 32 and a water pool 46 is present. For convenience of explanation, the fixing jig 30 and the angle fixing tool 38 are shown in cross section.

(6) Heat resistance

A drying test was carried out in accordance with JIS-L-0850 (1994) "Dry Heat tester method (A-2 method) for testing color fastness to Hot pressing", a test piece was prepared by cutting out a tape portion of a fastener chain, placing the test piece so that a water-repellent coating film was on the cotton side of a test stand, and a heating portion set at 150 ℃ was overlapped with 4kPa for 15 seconds, and the test piece was left at room temperature until the temperature became 30 ℃ or lower, and the test piece was peeled from the cotton to measure the area of resin adhering to the cotton, and the average value was determined by conducting 5 tests.

Heat resistance (%). attachment area ÷ pressure contact area × 100

The smaller the equivalent value, the more excellent the heat resistance.

< test example 2 >

Fastener chains F-31 to 47 were produced in the same manner as for fastener chain F-13, except that the amount and type of the additive in fastener chain F-13 of test example 1 were changed as shown in Table 3. Wherein, F-44 is a black zipper chain, and the rest is a white zipper chain. The additives newly used in test example 2 are as follows.

< additive >

Polycarbodiimide manufactured by Nisshinbo chemical Co., &lTtT transfer = L "&gTt L &lTt/T &gTt td., trade name" L A-1 "(number average molecular weight about 2000) (hereinafter referred to as" L A-1 ")

Polycarbodiimide: trade name "P-400" (number average molecular weight about 20000) (hereinafter referred to as "P-400") manufactured by Rhein Chemie

Ultraviolet absorber (benzophenone series): trade name "KEMISORB 10" (hereinafter referred to as "KEMISORB 10", manufactured by CHEMICRO KASEI Corporation)

Ultraviolet absorber (pigment-based titanium oxide): manufactured by DuPont corporation, trade name "TI-PURE (registered trademark) R101" (hereinafter referred to as "R101")

Ultraviolet absorber pigment (pigment-based carbon black): trade name "carbon Black # 45" (hereinafter referred to as "# 45") manufactured by Mitsubishi chemical corporation

Lubricant (fluorine-based resin lubricant) having a trade name of "KT L-450A" (hereinafter referred to as "KT L-450A")

[ Table 3]

The obtained fastener chain was evaluated for "colorability" and "heat resistance" by the same method as in test example 1. Further, evaluation of "bleeding property", "hydrolysis resistance", "light resistance after high-temperature and high-humidity treatment", and "sliding resistance" was performed by the following methods. The results are shown in Table 4.

(exudation)

The fastener chain was placed in a constant temperature and humidity chamber having a relative humidity of 90% at 70 ℃ and subjected to an exposure test for 1000 hours, and then the surface of the fastener chain was observed to evaluate the presence or absence of the oozing.

◎ no surface bleeding at all,

○ it is occult that the surface is partially exuded,

△ the exudation of the whole surface is observed,

×, bleeding over the entire surface was clearly observed.

(hydrolysis resistance)

The zipper chain was placed in a constant temperature and humidity bath at 70 ℃ and a relative humidity of 90%, and subjected to an exposure test for 1000 hours. The fastener chain after the test was subjected to a reciprocating opening and closing durability test with 10 times of opening and closing at MH level according to JIS S3015(2007), and subjected to an appearance evaluation.

◎ was completely unchanged.

○ -partial whitening is observed.

△ shows partial floating of the resin layer.

×, the resin layer deteriorated and peeling was observed.

(light resistance)

For a white fastener chain, a light resistance test by carbon arc light was carried out in accordance with JIS-L-0842 (2004) (3 rd exposure method), and b of the fastener chain before the light resistance test was carried out^*As a reference, the color difference Δ b was measured^*The color range of the white fastener chain before application of the water-repellent coating film was L^*a^*b^*(D65) Is numbered as L^*＝88.0～90.0、a^*＝-1.0～1.0、b^*Color measurement was performed using a spectrocolorimeter CM-3700A manufactured by KONICA MINO L TA, reflection measurement of SCI with a diameter of 5 × 7mm, and measurement of 15 points at 1CM intervals was performed by cutting out tape portions of the fastener chain, and the color difference Δ b was measured^*The average value of (A) was rated as light resistance as follows.

The black fastener chain F-44 was also subjected to the same light resistance test as the white test, and the color range of the black fastener chain before the application of the water-repellent coating film was L^*a^*b^*(D65) Is numbered as L^*＝19.0～21.0、a^*＝-1.0～1.0、b^*＝-1.0～1.0。

◎ less than 2.0

○ is more than 2.0 and less than 3.0

△ is 3.0 or more and less than 4.0

× ratio of more than 4.0

If less than 4.0, the level is practically unproblematic.

(light resistance after high temperature Multi-humidity treatment)

The fastener chain was placed in a constant temperature and humidity chamber having a relative humidity of 90% at 70 ℃ to perform an exposure test for 1000 hours, followed by the same light resistance test as described above.

(sliding resistance)

The sliding resistance was evaluated according to JIS S3015 (2007).

[ Table 4]

Claims (14)

1. A fastener chain having a structure in which fastener element rows of fastener elements are engaged with each other, the fastener element rows being attached along each side edge portion of a pair of fastener tapes each having a waterproof coating film formed on at least one main surface thereof, the waterproof coating film being formed of a polyester resin composition containing an aromatic polyester resin having one or two or more residues selected from the group consisting of an aliphatic dicarboxylic acid residue having 10 or more carbon atoms, an alicyclic dicarboxylic acid residue having 10 or more carbon atoms, an aliphatic diol residue having 10 or more carbon atoms, and an alicyclic diol residue having 10 or more carbon atoms,

the aromatic polyester resin contains 0.5 to 8 mol% of the total of the aliphatic dicarboxylic acid residue having 10 or more carbon atoms, 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, in the total of all acid component residues and all diol component residues.

2. The fastener chain according to claim 1, wherein 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 as a dimer acid residue.

3. The fastener chain according to claim 1, wherein the aromatic polyester resin has at least one of the aliphatic diol residue having 10 or more carbon atoms and the alicyclic diol residue having 10 or more carbon atoms as a dimer alcohol residue.

4. The fastener chain according to claim 2, wherein the dimer acid residue is a hydrogenated dimer acid residue.

5. The zipper chain of claim 3, wherein the diol residues are hydrodimer alcohol residues.

6. The fastener chain according to any one of claims 1to 5, wherein the polyester resin composition contains polycarbodiimide.

7. The fastener chain according to any one of claims 1to 5, wherein the polyester resin composition contains a lubricant.

8. The fastener chain according to any one of claims 1to 5, wherein the polyester resin composition contains at least one of an ultraviolet absorber and a pigment.

9. The fastener chain according to any one of claims 1to 5, wherein a content ratio of the aromatic polyester resin in the polyester resin composition is 60% by mass or more.

10. The fastener chain according to any one of claims 1to 5, wherein the fastener tape is made of a polyester resin.

11. The fastener chain according to any one of claims 1to 5, wherein the waterproof coating film enters into the irregularities of the main surface of the fastener tape at the interface with the fastener tape.

12. The fastener chain according to any one of claims 1to 5, wherein the waterproof coating film is dyed.

13. A slide fastener comprising the slide fastener chain according to any one of claims 1to 12.

14. An article provided with the slide fastener according to claim 13.

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