JPS5878517A - Net for breeding laver and coating agent therefor - 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 coatings for seaweed farmers or seaweeds.

As a coating material for seaweed cultivation nets, polyvinyl 7/l/
coh (PVA) and urea-formalin resin, PV
A type containing A, melamine-formalin resin, PVA and melamine acid colloid liquid is known. However, it has been revealed that formalin remains in the films formed by these coating materials and has an adverse effect on the adhesion and growth of seaweed spores.

In addition, as a coating agent that does not contain formalin, one containing PVA and glyoxal is known (Special Publications Publication No. 4).
6-1173), it is necessary to perform a heat treatment because a film with excellent water resistance cannot be obtained by drying in the sun alone after being applied to a mesh. For this reason, equipment for heat treatment is required, and seaweed cultivators cannot easily process the seaweed nets.

The present inventor has completed the present invention as a result of intensive research to develop a coating material that does not require heat treatment during surface treatment of nets and does not adversely affect the adhesion and growth of seaweed.

The present invention is a coating agent for seaweed cultivation nets or ropes containing polyvinyl alcohol and an organic titanium compound as active ingredients.

PVA preferably has a degree of polymerization of 2000 or more, and may be either completely saponified or partially saponified.

Organic titanium compounds include alkyl titanates such as tetraisopropoxytitanium (TPT), titanium chelates such as dihydroxybis(lacto)titanium (T
titanium acylates such as tri-n-butoxytitanium monostearate (TBS), di-n-butoxybis(triethanolaminate)titanium (TAT),
TA) etc.

When producing the coating material of the present invention, 5 to 1% of PVA is used.
Disperse in 5 times the amount of water and heat to 70° C. or higher while stirring to dissolve PVA, and then cool the solution to room temperature.

Separately, an organic titanium compound is dissolved in a solvent such as water or alcohol, and this solution is added to and mixed with the PVA solution. The amount of organic titanium compound added is 0.5 to 10% by weight of PVA.
, preferably 1 to 5%.

Since the coating material of the present invention gels if left for a long time, it is preferable to prepare it at the time of use.

If long-term storage is required, the PVA solution and the solution containing the organic titanium compound can be prepared and stored separately, and the two can be mixed or used sequentially at the time of use.

The coating agent of the present invention contains fertilizer for seaweed, inorganic salts such as disodium acid, organic substances such as amino acids, sugars, vitamins, etc.
Particularly preferred are the organic substances described in Japanese Unexamined Patent Publication No. 55-149567. As a thickener, water-soluble cellulose such as carboxymethyl cellulose and methyl cellulose,
Water-soluble polyhydroxy compounds such as partially neutralized polyacrylic acid can also be added.

As a method for applying the coating according to the present invention to aquaculture nets or ropes, for example, dipping or coating methods are used. The organic titanium compound and PV are then dried in the sun or by blow drying.
A reacts to form a water-resistant film.

Note that organic titanium compounds that are easily hydrolyzed, such as TP
When using T, TBSTA, etc., these compounds are dissolved in an organic solvent such as isopropanol, butanol, etc., and before use, after applying the PVA solution, apply the solution to a dried mesh, and dry it again. It is preferable to do so.

The coating material of the present invention does not require heat treatment when processing nets or ropes, and can form a film with excellent water resistance by drying in the sun or by blow drying. Further, since the coating agent of the present invention is insolubilized by a crosslinking reaction regardless of pH, an arbitrary pH can be selected depending on the type of seaweed, cultivation conditions, properties of additives, etc. Furthermore, the refractive strength of the net processed with the coating material of the present invention is enhanced, making it difficult for the net to lose its shape.
It has the advantage of making work at sea easier.

The coating agent of the present invention can be used for surface treatment of aquaculture nets or ropes for kelp, wakame, mozuku, etc. in addition to seaweed nets.

Parts in the examples below refer to weight.

Example 1 Add water to 60 parts of completely saponified PVA (degree of polymerization 2000 or higher), heat to 90°C or higher with stirring, and dissolve PVA.
800 parts of VA solution are obtained. After cooling this solution to around room temperature while stirring, add 6 parts of 50% TLA monoammonium salt solution and further add an appropriate amount of water to make a total volume of 1000.
Department.

The pH of this coating is approximately 7.

Example 2 Citric acid is added to the coating material of Example 1 to obtain a coating material whose pH is adjusted to 2.

Example 6 Add IJum (hydroxide) to the coating material of Example 1 and adjust the pH
A coating material adjusted to 12 is obtained.

Example 4 60 parts of partially saponified PVA (degree of polymerization 2000 or more) was used instead of the fully saponified PVA of Example 1, and the temperature was 75°C.
Coating material 100 having the same composition as in Example 1 was dissolved in
Obtain 0 parts O Example 5 8 parts of the PVA solution of Example 1 0 Process 2 parts of the isopropanol solution of leate and add an appropriate amount of water to make a total amount of 1000 parts.

Example 6 800 parts of the PVA solution of Example 1 was added with 0 of sodium nitrate.

2 parts and 0.0 parts dibasic sodium phosphate. Add 5 parts of 0 6 and adjust the pH to 10 with sodium hydroxide;
Add 3 parts of 0% TLA ammonium salt solution and an appropriate amount of water to make a total volume of 1000 parts.

Example 7 In addition to the components of Example 1, carboxymethyl cellulose 5
1000 parts and repeat the same procedure to make a total of 1000 parts.

Example 8 Add water to 60 parts of completely saponified PVA (degree of polymerization 2000 or more), dissolve in the same manner as in Example 1, and add an appropriate amount of water to bring the total amount to 1000 parts. liquid). Apart from this, TAT 0. Dissolve 5 parts of 0.0 in isopropanol to make a total of 100 parts (after drying, apply the second liquid and dry.

Example 9 Instead of TAT in Example 8, TB8TA 0. 0
Dissolve 5 parts in n-butanol to make a total of 100 parts and use it as a second liquid.

Comparative Example 1 To 800 parts of the PVA solution of Example 1, 10 parts of 40% methylated methylolmelamine, 2.5 parts of citric acid, and an appropriate amount of water were added to make a total amount of 1000 parts.

Comparative Example 2 To 800 parts of the PVA solution of Example 1, 50 parts of an acid colloid solution consisting of 12 parts of 50% methoxymethylolmelamine solution and 1.4 parts of 36% hydrochloric acid and an appropriate amount of water were added to make a total volume of 100 parts.
It will be 0 copies.

Comparative Example 3 Comparative Example 10 10 parts of 40% glyoxal was used instead of 40% methylated methylolmelamine, and the same procedure was carried out to make the total amount 1000 parts.

Test Example 1 Using net threads treated with the coating agents of Examples and Comparative Examples and dried in the sun for 6 hours, the number of attached spores was investigated by indoor incubation, and then cultured indoors to determine the size of seaweed after 10 days. compared. The results are shown in Table 1. All of the mesh yarns treated with the coating materials of Examples were good.

Table 1 Test Example 2 The coating materials of Examples and Comparative Examples were applied to seaweed nets, dried in the sun (6 hours), and then heat-treated at 90° C. for 20 minutes after drying in the sun. Net threads with a length of 5 crn were cut from these nets, immersed in boiling water for 5 minutes, and the unraveling of the threads was examined. The net thread is 6 pieces of Cremona No. 1 (Kuraray vinylon), 66 strands.
Real twisted yarn was used. In addition, a 6% PVA solution was used as a control.

The test results are shown in Table 2. In the table, the symbol A indicates that the threads have hardly changed, B indicates that the area near the cut surface has loosened slightly, C indicates that the area near the cut surface has loosened considerably, and D indicates that the entire thread has loosened.

The net threads treated with the coating agent of the present invention and the coating agent of Comparative Example 2 can be dried in the sun to obtain sufficient water resistance.

Table 2 Test Example 6 The hardness of the nets treated with the coating materials of Example 1 (A), Comparative Example 1 (Shun) and Comparative Example 4 (C5) was investigated by 20 seaweed farmers. Nori net (1.5 x 18
Two pieces of each were used: 66 threads of Cremona No. 1 (early silk thread: 42 threads of Cremona No. 1, 42 threads of Cremona No. 1, and 120 threads of Cremona No. 1). As a result, in order of hardness, 16 people judged it to be ABC, and 4 people judged it to be CAB. There was found.

Applicant: Daiichi Seine Co., Ltd. Agent: Patent attorney Masamichi Kobayashi Procedural amendment (voluntary) December 20, 1982 Kazuo Wakamatsu, Commissioner of the Patent Office 1.Display of the incident Patent Application No. 170149/1983 3. Person who makes corrections Relationship to the incident: Patent applicant address 4. Deputy manager 5. Date of amendment order 6. Number of inventions increased by amendment 8. Contents of amendment As per the attached correction sheet Correction book The following corrections will be made in the specification.

1, page 4, line 8, “Compounds can also be added.”
amended as follows.

Compounds, alginic acid, etc. can also be added.These thickeners not only increase the viscosity, but also modify the flexibility of the film, and also react with organic titanium compounds to increase the
Together with VA, it constitutes a part of the water-resistant coating.

2, page 4, line 9, "coating according to the present invention" is changed to "coating agent according to the present invention".

3. Change "Comparative Example 4" to "Comparative Example 2" on page 16, line 2.

4. Add "(sun-dried)" after "processed net" on page 13, line 3.

5. On page 1.3, line 8, "FABC and Judgment" is changed to "ACB and Judgment."

Claims (1)

[Claims] A coating agent for seaweed cultivation nets or ropes containing polyvinyl alcohol and organic titanium compounds as active ingredients.