JPS6039481A - Anti-stain coated yarn - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stain-proof coated yarn that can be suitably used for stain-proof fishing nets, fishing net ropes, etc. Antifouling coated yarn having excellent antifouling properties and durability, which is coated with a vinyl chloride resin sol composition containing a large amount of copper or/and copper compound powder and a plasticizer, and gelled. It is related to.

In the fisheries industry, aquaculture fisheries and set-net fisheries have become popular since the 200-yield era.

In this type of fishing, the fishing nets are left in the sea for long periods of time, from several months to a year, so a lot of seaweed and fish and shellfish adhere to the fishing nets, and as a result of this so-called contamination, the meshes of the nets become narrow and the nets become unusable. As the passing tide worsens, the inside of the fishing net becomes darker. In such a state, it becomes difficult for the fish to enter the net. In addition, in the case of aquaculture, growth becomes poor and sometimes the farmed fish die.

Traditionally, in order to prevent seaweed and fish and shellfish from adhering to fishing nets,
Various antifouling methods have been implemented.

For example, there is a method of applying a paint containing an organic tin compound as an antifouling agent to fishing nets. This method has recently become a pollution problem because the paint is highly toxic and emits a strong irritating odor when applied, and the desired antifouling effect is not very good either. .

In addition, we process fibers made by twisting copper wire with filaments such as polypropylene, polyethylene, nylon, etc., and threads made by dispersing copper powder filaments into antifouling ropes and nets for fishing, aquaculture fishing, and fixed nets. Used for fishing. However, all of these have insufficient antifouling effects due to the small amount of copper eluted, and furthermore, when twisted with copper shields, the copper wire is hard and difficult to process, such as making rope. Additionally, during use, the copper wire is corroded and degraded by seawater, resulting in poor durability.

In addition, the amount of copper eluted from fishing silk or nets obtained by dispersing copper powder into polyethylene or the like and spinning it into yarn has a much smaller amount of copper, making it impractical for use in antifouling ropes and nets. Significant improvements are desired.

The present inventors have discovered a material that has excellent stain resistance (for example, for three years), is easy to process into covered yarn, and is easy to process when the covered yarn is processed into ropes or nets. As a result of various researches aimed at providing stain-resistant coated yarn that exhibits excellent performance in terms of durability (e.g., mechanical strength) of the net, it was surprisingly discovered that specific types and amounts of copper or When using a coated yarn in which the core yarn is coated with a vinyl chloride resin sol composition containing a fine powder of a copper compound and a plasticizer, and a coating layer is formed by gelling the core yarn, the above-mentioned problems occur. It was discovered that these problems could be solved all at once, and the present invention was completed.

That is, the present invention provides a coated yarn in which a core yarn is coated with a vinyl chloride resin sol composition and the same is gelled, in which the vinyl chloride sol composition contains 100 parts by weight of the vinyl chloride resin. The present invention provides an antifouling coated yarn characterized by containing 40 to 400 parts by weight of copper or/and copper compound powder having an apparent specific gravity of 4 or less and 40 to 150 parts by weight of a plasticizer.

Other objects and advantages of the invention will become more apparent from the following description.

The vinyl chloride resin used in the vinyl chloride 41ij fat sol trap in the present invention is usually obtained by emulsion polymerization, seeded emulsion polymerization, etc. of monomers such as vinyl chloride monomer, vinyl chloride and vinyl acetate, etc., in view of the viscosity stability of the sol. Alternatively, it is a so-called resin for vinyl chloride paste obtained by drying an emulsion of resin powder obtained by emulsion suspension polymerization using a spray dryer, etc., and the content of vinyl chloride is 60%.
It refers to a material containing 60 weight factor or more in the total resin, preferably 70 weight factor or more, more preferably 80 weight factor or more, and these include, for example, an average polymerization degree of 800 to 80 weight factor or more. Homopolymer resin for pasting of vinyl chloride of 2000, copolymer resin for pasting with vinyl acetate having a vinyl chloride content of 80% by weight, or 8.
Examples include a blend resin of a vinyl chloride vest resin containing 60 weight percent of vinyl chloride and a normal vinyl chloride resin obtained by a suspension polymerization method.

In the powder of copper or/and copper compound as used in the present invention: copper powder refers to powder with a copper content of 98% by weight or more;
Copper compound powders include cuprous oxide, copper sulfate, cupric oxide, copper acetate, cupric tartrate, cupric chloride, etc. containing copper as a main component, preferably cuprous oxide or copper sulfate, and especially copper compound powder. Like/
or cuprous oxide powder;
0 mesh passing amount is 95 weight windward, preferably 140
Metush passing distance is 95 weight upwind, more preferably 20
Q mesh passing amount is 95 weight upwind, particularly preferably 2
The amount of 50 mesh passing through is 95 weight upwind. The copper or/and copper ratio powder may be one or two selected from the group consisting of copper powder, cuprous oxide, and copper sulfate.
It is preferable to use a powder having a dendritic form, which has a 14° mesh passing through a 14° mesh of 95 gw, and has a dendritic form in view of its dispersibility as a vinyl chloride-based sol composition.

Further, the above-mentioned copper or/and copper compound powder needs to have an apparent specific gravity (measurement method JIS K-6721) of 4 or less. Copper or/and copper compound powder,
If the apparent specific gravity exceeds 4, there will be a tendency for it to settle in the vinyl chloride resin sol, or there will be a tendency for it to settle in the coating nozzle during the process of coating the core yarn with the vinyl chloride resin sol composition. The surface skin of the coated yarn (coating layer,
) is undesirable because it becomes difficult to obtain a stain-resistant coated yarn having the above-mentioned excellent properties.

Further, the amount of copper or/and copper compound powder having an apparent specific gravity of 4 or less is 40 to 40 parts by weight per 100 parts by weight of vinyl chloride resin.
It is good to use 400 parts by weight, preferably 5 to 60 to 300 mfL parts, particularly preferably 100 to 250 parts by weight. If the amount of the powder used is less than 40 parts by weight, the antifouling property and its durability tend to deteriorate, which is undesirable. On the other hand, if the amount exceeds 400 parts by weight, it may cause lumps in the coated nozzle as described above. This is because the so-called spinnability deteriorates and becomes undesirable.

The plasticizer used in the vinyl chloride fruit resin sol and composition in the present invention is not particularly limited as long as it is compatible with the vinyl chloride resin used in the present invention, and may be used as appropriate depending on the purpose. It is possible to select the type and use it alone or in combination in a range of 40 to 150 parts by weight per 100 parts by weight of vinyl chloride resin. It is preferable to use a phthalate ester-based and/or adipic ester-based plasticizer as a plasticizer that provides a vinyl resin sol composition and effectively improves the adhesion with the core thread, and the amount of the plasticizer used is It is preferably 50 to 130 parts by weight, particularly preferably 60 to 120 parts by weight.

If the amount of plasticizer is less than 40 parts by weight, the viscosity of the vinyl chloride resin sol composition will increase and the yarn protection properties will deteriorate, which is undesirable. On the other hand, if it exceeds 150 parts by weight,
This is not preferred because the adhesion between the core yarn and the coating layer decreases, making it difficult to obtain a stain-resistant coated yarn with excellent durability such as mechanical strength.

The above-mentioned phthalate ester plasticizers include octyldecyl phthalate, dinonyl phthalate, diterethylhexyl phthalate, diisooctyl phthalate, moro-octyl phthalate, dinonyl phthalate, diisodecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, Examples include butylbenzyl phthalate, butyl lauryl phthalate, and among these, diterethylhexyl phthalate, diyne octyl phthalate, moro-octyl phthalate, butylbenzyl phthalate, and octyldecyl phthalate are preferably used.

In addition, examples of adipate ester plasticizers include dioctyl adipate, diisodecyl adipate, dioctyl azelaate, dibutyl sebacate, dioctyl sepacate, etc. Among these, in particular,
Dioctyl adipate is preferably used.

Although the reason is not clear, the above-mentioned specific conditions of the vinyl chloride resin, copper or/and copper compound powder, and plasticizer act synergistically, resulting in the present invention having the above-mentioned excellent performances. It is believed that a stain-resistant coated yarn can be obtained.

In the present invention, if desired, in addition to the above-mentioned components, the types and amounts of components of the vinyl chloride resin sol composition may be appropriately selected, such as stabilizers, stabilizing aids, and enhancers. Adhesives, antioxidants, gelling agents, diluents, colorants,
Antifungal agents, antialgal agents, coupling agents, etc. can be used.

Examples of the above stabilizers and stabilizing aids include:
Calsulam/zinc type, calsulam/zinc organic complex, barium/zinc type, zinc type complex, epoxy co-stabilizer, organotin mercaptite.

Organotin octyl, organotin laurate, organotin malate,
Organotin methyl, dibasic lead phosphite, etc. can be mentioned, and such stabilizers are used alone or in combination, for example, about 0.1 to about 10 parts by weight per 100 parts by weight of vinyl chloride resin. It is possible to show the amount used.

Types of thickeners include, for example, rushum carbonate, barium sulfate, kaolin clay, silica powder, mica, titanium white, caneum earth, aluminum hydroxide, etc., but calcium carbonate is preferable, e.g. , Hakuenka CcR, Wheaton SB, Sedimentary Charcoal, NC
Examples include C1110. Such thickeners may be used alone or in combination in an amount of, for example, about 5 to about 30 parts by weight per 100 parts by weight of the vinyl chloride resin.

Examples of the type of antioxidant include 2,6-di-t-
Antioxidants such as butyl-4-methylphenol, 2,2-methylenebis(6-t-butyl-4-ethylphenol), and dilaurylthiodipropionate may be mentioned; For example, about 0.1 to about 1 per 100 parts by weight of vinyl chloride resin, alone or in combination.
．． Usage amounts such as 0 parts by weight can be indicated.

Examples of the gelling agent include aluminum stearate, silica airgel, amine-modified montmolinite, and E-CON 100 (manufactured by Nippon Zeon). Such gelling agents may be used alone or in combination, for example. About 0.5 to about 3 per 100 parts by weight of vinyl chloride resin
Amounts used may be indicated, such as parts by weight.

Examples of diluents include mineral spirits,
Examples include kerosene, xylene, toluene, rubber solvent, etc. Such diluents may be used alone or in combination in an amount of, for example, about 2 to about 20 parts by weight per 100 parts by weight of the vinyl chloride resin. can be shown.

Examples of the types of colorants include phthalocyanine blue, phthalocyanine green/, Noonsa Yellow, alizarin lake, titanium oxide, zinc white, permanent red, carbon black, and quinacridone. Alone or in combination, for example, about o, oot to about 5 parts by weight per 100 parts by weight of vinyl chloride resin.
．． Usage amounts such as 0 parts by weight can be indicated.

Examples of the types of antifungal agents and antialgal agents include 2.4°5.
6-titrachloroisophthalonitrile, 10°10'-
Oxybisphenoxyarsine, 2-(4-thiazolyl)-benzimidazole, tributyltin laurate, N
(Fluocyclomethylthio)phthalimide, N-dimethyl-N'-phenyl-(N'dichlorochloromethylthio)-sulfamide, etc. can be mentioned, and such fungicides and algaecides can be used alone or in combination, For example, the amount used may be about 1 to about 10 parts by weight per 100 parts by weight of the vinyl chloride resin.

The core yarn used in the present invention provides the desired tensile strength (for example, 3 f/de or more) as a coated yarn for fishing nets, etc., and contains powder of copper or/and a copper compound with an apparent specific gravity of 4 or less. There are no particular restrictions on the material as long as it can be coated with the vinyl chloride resin sol composition.

However, from the viewpoint of mechanical strength such as tensile strength, the denyl is preferably 50 to 2,500 denyl. If the denier is too small (less than 50), the yarn will not have strength and will easily break when braided into a fishing net, while if it exceeds 2,500 denier, the yarn will become very thick when braided into a fishing net, which is undesirable. In particular, those having 100 to 1900 denyl can be suitably used.

Furthermore, the core yarn is coated with the vinyl chloride resin sol composition according to the present invention, and has heat resistance that can withstand the processing temperature during gelling, so that it can be used as an antifouling fishing net, etc. It is preferable to use materials that have excellent dimensional stability when used and flexibility during processing, such as polyester, nylon, rayon,
Examples include multifilaments, twisted yarns, and monofilaments such as polypropylene, polyethylene, and acrylic, with polyester and nylon being particularly preferred.

In the present invention, a vinyl chloride resin powder, a powder of copper or/and a copper compound having an apparent specific gravity of 4 or less), and a plasticizer (01
Other additives that can be added as necessary can be blended by a mixing method known per se.

It is preferable to disperse it as uniformly as possible, for example,
pony Mixer, Change-can
Mixer, Hober Mixer.

The vinyl chloride resin sol composition of the present invention can be obtained using a mixing means such as a Butterfly Mixer or an LLI crusher. At this time, air bubbles are often mixed into the sol composition, but in such cases, defoaming can be carried out using a stirring type or dropping type defoaming device.

The antifouling coated yarn according to the present invention is produced by dipping, for example, a nylon multifilament as a core yarn into the vinyl chloride resin sol composition obtained by the above-mentioned mixing method.
The stain-resistant coated yarn with nylon multifilament as the core yarn can be easily made by passing it through a sizing nozzle with a fin diameter of φ, heating it in a heating furnace at about 190°C to gel it, and then applying a coating layer and cooling it with water. can be obtained.

In addition, as for the antifouling coated yarn, the weight ratio of the core yarn of the coated yarn to the coating layer made of the vinyl chloride resin sol composition is preferably 5 to 35% by weight, particularly preferably 5 to 20% by weight.
On the other hand, the amount of the coating layer is preferably 95 to 65% by weight, particularly preferably 95 to 80% by weight. If the width of the core yarn is less than 5% by weight, spinnability deteriorates and it becomes difficult to obtain a product with a smooth surface, which is undesirable.If the width of the core yarn exceeds 35% by weight, the copper or/and copper compound powder This is because the persistence of copper ion elution becomes short, which is not desirable.

The antifouling coated yarn according to the present invention can be processed into any shape and used for fishing nets, fishing net ropes, etc., and it not only has excellent antifouling properties, but also has excellent mechanical strength, etc., which is desired for fishing applications. In addition, it is flexible and contains a suitable amount of copper or/and copper compound powder, so it is suitable for sedimentation and can be widely used for fishing purposes.

EXAMPLES Hereinafter, the excellent performances of the antifouling coated yarn of the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, the test method and evaluation were performed according to the following.

Test method ■ Copper elution rate (μt/c#l 1 day) 500 cc of seawater was placed in a 1 ton beaker, and the diameter of the covered thread was measured in advance to calculate the surface area (Cctl), which was 9 m in length.
After adding the coated yarn and continuing to stir gently for 24 hours at a temperature of 25°C, 50cc of seawater in which copper ions were eluted was added.
The amount of copper (μf) in the collected seawater was used to calculate the copper elution rate using a conventional colorimetric method.

■ Tensile strength (1 piece) and tensile elongation ((6) length 20
A 0m coated yarn was used as a sample, and the test piece was pulled at a tensile speed of 200
■ Tensile at /min, strength at cutting f) and elongation (
The tensile strength (f/*) and tensile elongation (@) were calculated using a conventional method.

(2) Adhesion between the core yarn and the covering layer, smoothness and flexibility of the covering yarn surface Judgment was made from a manual peel test of the covering layer and a tactile smoothness and flexibility test, and the results were categorized and evaluated as follows.

○...Excellent D...Good
40) in a mixer, and while rotating the mixer, 1 part by weight of 30 di-2-ethylhexyl phthalate (hereinafter abbreviated as DoP) and 1 part by weight of di-2-ethylhexyl phthalate (hereinafter abbreviated as DoP) were added to 100 parts by weight of the vinyl chloride paste resin. 20 parts by weight of ethylhexyl adipate (hereinafter abbreviated as DOA), liquid Ca-Zn
3 parts by weight of system stabilizer (hereinafter abbreviated as Ca-Zn),
Isopropyltriisostearoisotitanate (hereinafter referred to as
After adding 0.5 parts by weight of 1p-1i5i-i'l' and continuing stirring for 30 minutes, copper powder (manufactured by Fukuda Metal Foil & Powder Industry ■; cE-115; apparent specific gravity approximately 1.6) was added. ')
60 parts by weight of calcium carbonate (hereinafter abbreviated as CLI) and 10 parts by weight of calcium carbonate (manufactured by Shiraishi Kogyo ■; Hakuenka CC-R) were gradually added, and stirring was continued for an additional 60 minutes to prepare a vinyl chloride resin sol composition. .

Next, a 420 denier nylon 6 multifilament was immersed in the above vinyl chloride resin sol composition and passed through a sizing nozzle with a hole diameter of 0.7 wmφ.
The vinyl chloride resin sol composition was gelled in a heating furnace at 90°C and cooled with cold air, so that the core yarn was 14% by weight and the coating layer was 8% by weight.
A 6% by weight coated yarn of 3130 denier was obtained.

The results of measuring various performances of the covered yarn are shown in Table 2 of Table 1.

The coated yarn of the present invention not only has excellent spinnability, but also has excellent balanced performance in adhesion between the core yarn and the coating layer, smoothness of the coated yarn surface, flexibility, tensile strength, and tensile elongation. demonstrate,
Furthermore, it also exhibited excellent antifouling properties due to its excellent copper dispensing rate.

Examples 2 to 10 and Comparative Examples 1 to 7 As shown in 1 of Table 1 and 1 and 1 of Table 2, Example 1
A vinyl chloride resin sol composition was obtained in the same manner as in Example 4, a plasticizer, a stabilizer, a coupling agent, and a diluent mineral spirit lang part were added; in Example 7, a plasticizer was added. It was prepared by adding 12 parts by weight of pasty carbon as a pigment together with the agent, stabilizer, and coupling agent. Furthermore, the core thread shown in 2 of Table 1 of Fang and 2 of Table 2 of Iku,
A covered yarn having a fineness expressed in terms of nozzle and heating furnace temperature, a core yarn weight ratio, and a coating layer weight ratio of 1 was obtained in the same manner as in Example 1.

In addition, in the "Product name" section of "Powder of copper or/and copper compound" in 1 of Table 1 and 1 of Table 2 of Fang, rcU, OJ
is cuprous oxide manufactured by Nichiken Chemical Industry Co., Ltd., with a specific gravity of approximately 13, with 98% or more passing through a 325 mesh sieve.

As shown in Table 2 of λ・1, the coated yarn according to the present invention was a stain-resistant coated yarn showing excellent performance similar to that of Example 1, but Comparative Examples 2.3.5 and 7 Comparative Example 1
, 4 and 6 were particularly poor in copper elution rate and were not suitable for practical use as antifouling coated yarns, or were poor in spinnability, surface smoothness of coated yarns, etc. and were not suitable for practical use.

Further, when using only a copper wire with a diameter of 200μ, the copper elution rate only showed a value of 2.

Claims (1)

[Scope of Claims] 1) A coated yarn in which a core yarn is coated with a vinyl chloride resin sol composition and this is gelled, in which the vinyl chloride resin sol composition is Powder of copper or/and copper ratio compound having an apparent specific gravity of 4 or less 40~
An antifouling coated yarn characterized by containing 400 parts by weight and 40 to 150 parts by weight of a plasticizer. 2) The weight ratio of the core yarn of the covered yarn to the coating layer made of the vinyl chloride resin sol composition is 5 to 35 weight percent of the core yarn and 95 to 65 weight percent of the core yarn, claim 1. The stain-resistant coated yarn described.