JP2002265849A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition having no stiffness, excellent installation workability, excellent adhesivity to a fishing net and less reduction in antifouling properties by peeling of the coating film when applied to the fishing net. SOLUTION: This coating composition is characterized in that the coating composition comprises an acrylic resin (A), cuprous suboxide (B) and a silicone oil (C), the acrylic resin (A) has >=50,000 weight-average molecular weight and <=-10 deg.C glass transition temperature, the cuprous suboxide (B) mixed has the mass ratio of a resin solid content in the coating composition to the cuprous suboxide of [resin]/[cuprous suboxide (B) in a range of 40/60 to 65/35 and the silicone oil (C) mixed has the mass ratio of the resin solid content in the coating composition to the silicone oil of [resin]/[silicone oil (C)] of 99/1 to 70/30.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a paint composition used for fishing nets and the like in the field of aquaculture, and more particularly to a coating composition having excellent adhesion to fishing nets when used for fishing nets and the like.
The present invention relates to a coating composition capable of obtaining a coating film without cracks.

[0002]

2. Description of the Related Art Fish nets, underwater structures, and the like are exposed to water for a long period of time, and on the surface thereof, such as helminths such as hydroids, shellfish, sessile polychaetes, seaweeds, bryozoans, mollusks, etc. Efforts are made to maintain these marine organisms with great effort and expense, as they grow and spread. Conventionally, organotin polymers have been widely used to prevent the adhesion of marine organisms. However, due to their strong toxicity, low-toxic antifouling agents have been desired in view of the environment.

[0003] Japanese Patent Application Laid-Open No. 6-25560 discloses an antifouling paint composition having low toxicity and high safety to the human body containing copper pyrithione and cuprous oxide.
This antifouling paint composition is also excellent in long-term storage stability without gelation.

Japanese Patent Application Laid-Open No. 2000-264804 discloses that
An antifouling composition comprising a soluble copper glass and a metal pyrithione is disclosed. The antifouling composition describes that at least one binder resin selected from the group consisting of acrylic resin, vinyl resin, modified vinyl resin, styrene-butadiene resin and polysiloxane resin can be used, It has a long-term antifouling effect.

Japanese Unexamined Patent Publication No. 9-176577 discloses an antifouling paint composition effective for preventing the attachment of shellfish and hydro-insects to hulls, fishing nets and underwater structures, and polyether-modified silicones of HLB2 to HLB7. One containing cuprous oxide is disclosed.

However, when a fishing net was treated with the above-described antifouling paint composition, the fishing net was dull and only a hard coating film was obtained. In addition, it may have poor adhesion to fishing nets, and the film may fall off while being folded or suspended before being installed in a fishing ground, resulting in a decrease in antifouling properties. Was.

[0007]

SUMMARY OF THE INVENTION An object of the present invention, when applied to a fishing net or the like, is that it has less burrs, is excellent in installation workability, has excellent adhesion to the fishing net, and has a low antifouling property due to peeling of the coating film. An object of the present invention is to provide a coating composition having a small amount.

[0008]

The present invention provides a coating composition comprising an acrylic resin (A), cuprous oxide (B) and a silicone oil (C), wherein the acrylic resin (A) comprises:
The weight average molecular weight is 50,000 or more, and the glass transition temperature is-
10 ° C. or less, and the cuprous oxide (B) has a mass ratio of [resin] / [cuprous oxide (B)] = 40/60 to 65/35 with respect to the resin solid content in the coating composition. The silicone oil (C) has a mass ratio to the resin solid content of the coating composition of [resin] /
[Silicone oil (C)] = a coating composition characterized by being blended in the range of 99/1 to 70/30.

[0009] The coating composition further contains an organic antifouling agent, and the organic antifouling agent has a mass ratio to the cuprous oxide (B) of [cuprous oxide (B)]. / [Organic antifouling agent] = 70/30 to 98/2. The organic antifouling agent is copper pyrithione, and the mass ratio of the copper pyrithione to cuprous oxide (B) is [cuprous oxide (B)] / [copper pyrithione] =
More preferably, it is blended in the range of 85/15 to 95/5. Further, the silicone oil (C) is preferably a polyether-modified silicone oil.
The above coating composition can be suitably used for an antifouling paint for fishing nets. Hereinafter, the present invention will be described in detail.

[0010] The coating composition of the present invention contains an acrylic resin (A). The acrylic resin (A)
The weight average molecular weight is 50,000 or more. If it is less than 50,000,
Poor adhesion when applied to fishing nets. Preferably it is in the range of 80,000 to 300,000. If it exceeds 300,000,
The viscosity of the paint increases, resulting in poor workability.

The acrylic resin (A) has a glass transition temperature (Tg) of -10 ° C. or less. If it exceeds -10 ° C, when applied to fishing nets, the adhesion will be insufficient. Preferably it is -15C or less. The above glass transition temperature (T
g) can be determined by calculation from the types and amounts of the monomers constituting the acrylic resin (A).

As the acrylic resin (A), those obtained by subjecting an acrylic monomer and, if desired, other monomers to solution polymerization such as ordinary radical polymerization can be used. Examples of the acrylic monomer used in the above method and other monomers used as desired include, for example, (meth) acrylates,
Methyl (meth) acrylate, ethyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth)
The carbon number of the ester part such as stearyl acrylate is 1 to 2
(Meth) acrylic acid alkyl ester of 0; 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc., having 1 to 2 carbon atoms
A hydroxyl-containing (meth) acrylic acid alkyl ester of 0;
(Meth) acrylic acid cyclic hydrocarbon esters such as phenyl (meth) acrylate and cyclohexyl (meth) acrylate; unsaturated monobasic acids such as (meth) acrylic acid, maleic acid and its monoalkyl esters, itaconic acid and Unsaturated dibasic acids such as monoalkyl esters and monoalkyl esters thereof, maleic acid adduct of 2-hydroxyethyl (meth) acrylate, phthalic acid adduct of 2-hydroxyethyl (meth) acrylate, (meth) acryl Carboxyl group-containing acrylic monomers such as dibasic acid adducts of unsaturated monobasic hydroxyalkyl esters such as succinic acid adducts of 2-hydroxyethyl acid; (poly) ethylene glycol mono (meth) acrylate;
(Poly) alkylene glycol esters of (meth) acrylic acid such as 10 polyethylene glycol mono (meth) acrylates; and, in addition to alkoxyalkyl (meth) acrylates having 1 to 3 carbon atoms, (meth) acrylamide;
Vinyl compounds such as styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl toluene and acrylonitrile; and crotonates; unsaturated dibasic acids such as maleic diesters and itaconic diesters Can be mentioned. These monomers may be used alone,
More than one species may be used in combination.

[0013] The coating composition of the present invention contains cuprous oxide (B). The cuprous oxide (B) is blended in a weight ratio of the resin solid content in the coating composition of [resin] / [cuprous oxide (B)] = 40/60 to 65/35. It is. If the amount of cuprous oxide (B) is smaller than the above range, the antifouling property becomes insufficient. If the amount of cuprous oxide (B) is too large, when applied to fishing nets, the adhesion is not good, and the resulting fishing nets are hardened, resulting in cracks.

[0014] The coating composition of the present invention contains a silicone oil (C). The above silicone oil (C)
Is preferably a polyether-modified silicone oil because of its excellent antifouling effect on aquatic organisms such as barnacles. The silicone oil (C) is blended in a mass ratio of [resin] / [silicone oil (C)] = 99/1 to 70/30 with respect to the resin solid content in the coating composition. . If the amount of the silicone oil (C) is smaller than the above range, the adhesion due to the acrylic resin (A) remains, resulting in poor installation workability. If the amount of the silicone oil (C) is too large, the adhesiveness becomes insufficient when applied to fishing nets.

The coating composition of the present invention preferably contains another antifouling agent in addition to the cuprous oxide (B). By using other antifouling agents in combination, the types of aquatic organisms that exhibit antifouling effects can be greatly expanded. As the other antifouling agent, an organic antifouling agent is preferable.

Examples of the organic antifouling agent include manganese ethylenebisdithiocarbamate (maneb), zinc dimethyldithiocarbamate (ziram),
Zinc ethylene bisdithiocarbamate (Zineb), 2
-Methylthio-4-tert-butylamino-6-cyclopropylamino-S-triazine (Irgarol 105
1), 2,4,5,6-tetrachloroisophthalonitrile (Nopcoside N96), N, N-dimethyldichlorophenylurea (DCMU), rodan copper, 4,5-dichloro-2-n-octyl-3 (2H ) -Isothiazoline (SEEANINE 211), N- (fluorodichloromethylthio) phthalimide (Priventol A-3),
N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide (Priventol A
4S), N-dichlorofluoromethylthio-N ', N'
-Dimethyl-Np-tolylsulfamide (Priventol A5S), 2-pyridinethiol-1-oxide copper salt (kappa-pyrithione), 2,3,5,6-tetrachloro-4- (methylsulfonyl) Pyridine (Densi
l S100), 3-Iodo-2-propynyl butyl carbamate (TROYSAMPOLYPHASE P
100), diiodomethylparatolyl sulfone (AMI
CAL 48), bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate (bisdaisen),
Pyridine-triphenylborane (PK) and the like can be mentioned.

Further, triphenylborane-amine complex compounds such as stearylamine-triphenylborane and laurylamine-triphenylborane; triphenylborane-alkoxy groups such as 3- (2-ethylhexyloxy) propylamine-triphenylborane Containing amine complex compound; thiuram-based compounds such as tetraethylthiuram disulfide and tetrabutylthiuram disulfide can also be used.

The mass ratio of the organic antifouling agent to cuprous oxide (B) is [copper oxide (B)] / [organic antifouling agent].
= 70/30 to 98/2. If the amount of the organic antifouling agent is more than the above range, the cost becomes too high. When the amount of the organic antifouling agent is too small, no combined effect is observed.

In the present invention, copper pyrithione is preferred among the other antifouling agents. When copper pyrithione and cuprous oxide (B) are used in combination, an antifouling effect on aquatic organisms, particularly barnacles, can be effectively exhibited, and when the amount of cuprous oxide (B) is small, Even with this, an excellent antifouling effect can be obtained.

The above copper pyrithione has a mass ratio to the cuprous oxide (B) of [cuprous oxide (B)] / [copper pyrithione].
= 85/15 to 95/5. If the amount of copper pyrithione is too large, the cost will be too high. When the amount of copper pyrithione is too small, no combined effect is observed. The above cuprous oxide (B)
Is 25 to 60 with respect to the solid content of the coating composition.
Although it can be used as long as it is within the range of mass%, when the cuprous oxide (B) and copper pyrithione are used in combination, good antifouling property can be obtained with a smaller amount of the cuprous oxide (B). it can. Reducing the amount of the antifouling pigment is advantageous in terms of adhesion and cracking, and is also advantageous in reducing net dyeing workability and net weight by reducing Cu ₂ O having a high specific gravity.

The coating composition of the present invention contains, in addition to the acrylic resin (A), a vinyl chloride / vinyl acetate copolymer,
Synthetic resin such as vinyl chloride / alkyl vinyl ether copolymer, vinyl resin such as vinyl chloride resin, alkyd resin, urethane resin, polyester resin, synthetic rubber, chlorinated polyethylene; wood rosin, gum rosin,
Natural resins such as rosin resins such as denatured rosin and rosin ester may be contained as vehicles. The other vehicle is 30% by mass in the solid content of the coating composition.
It is preferably at most 20% by mass, more preferably at most 20% by mass, more preferably at most 10% by mass.

In addition to the silicone oil (B), dissolution aids such as petrolatum, paraffins, polybutene, and polysulfide may be further added to the coating composition of the present invention. Coloring pigments, extenders and the like generally used in coating compositions can be blended with the above-mentioned coating compositions. The color pigment is not particularly limited, and examples thereof include titanium oxide, carbon black, red iron oxide, phthalocyanine blue, phthalocyanine green, and quinacridone. The extender is not particularly limited, and examples thereof include zinc white, talc, clay, precipitated barium sulfate, and calcium carbonate.

The coating composition may further contain a known additive such as a plasticizer such as dioctyl phthalate; a flow controlling agent such as organic bentonite and colloidal silica. An elution aid other than the silicone oil (B),
The compounding amount of the pigment and other additives is preferably 30% by mass or less, more preferably 20% by mass or less, in the solid content of the coating composition.

The coating composition of the present invention can be produced by blending and mixing the above components. The mixing method, mixing order, and the like of each component and additive can be performed by various methods. The coating composition prepared as described above can be applied to fishing nets, ships, underwater structures, and the like by various coating methods such as dip coating and spray coating. When applied to fishing nets, dip coating is preferred. Thereafter, the solvent can be volatilized and removed at room temperature or under heating to form a dried coating film.

The coating composition of the present invention can be suitably used for fishing nets such as aquaculture nets and fixed nets, fishing net accessories and the like. By applying the coating composition of the present invention to fishing nets and the like, it is possible to obtain a flexible coating film with less burrs and tackiness, so that it is excellent in installation workability in a fishing ground, and excellent in adhesion to a fishing net, The antifouling property due to peeling of the coating film is not reduced. This is because the acrylic resin (A) has a low T
Because of the high molecular weight in g, the tackiness of the acrylic resin (A) allows pigments such as cuprous oxide (B) to adhere to fishing nets and at the same time suppresses the surface tackiness with silicone oil floating on the surface. It is presumed that it has excellent workability and becomes a flexible coating film. Furthermore, by combining copper pyrithione with cuprous oxide (B), antifouling properties against various aquatic organisms, particularly barnacle resistance, can be ensured. Further, Cu ₂ O having a high specific gravity can be reduced. INDUSTRIAL APPLICABILITY The present invention can prevent the adhesion of aquatic organisms such as barnacles, kanase kanashi, shiroboya, serpura, mussels, scorpion beetles, aonori and aosa.

[0026]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Parts represent parts by mass. Examples 1 to 8, Comparative Examples 1 to 7 Components other than the silicone oil shown in Table 1 were blended,
The mixture was dispersed with a G mill to prepare a dispersion base. Thereafter, silicone oil was added and the mixture was stirred with a disper to prepare each coating composition. The units of the components in Table 1 are parts by mass. In Table 1, each component used the product shown in Table 2. Silicone oil PA-01 is a polyether-modified silicone oil, silicone oil KF96-100.
Is a polydimethylsiloxane. In Table 1, "res
“in / Cu ₂ O” represents a solid content ratio of resin / cuprous oxide,
“Resin / silicone” represents the solids ratio of resin / silicone oil.

The following evaluation method was carried out using the obtained coating composition.
It was evaluated according to the law. The results are shown in Table 1.Evaluation method  (1) Adhesiveness Six sections, 60 pieces, 400 deniers, which were subjected to an ordinary dip coating process
And dry the polyethylene knotless net at 20 ° C for 24 hours.
After that, hook it on a 2cm diameter metal rod and move it up and down.
The presence or absence of peeling was examined. Peeling area: 5% or less ○, 5-1
0% ○-△, 10-20% ２０, 20% or more ×. (2) Adhesion The dip coating treatment was performed using the same net as in (1) above,
Hold the net dried at 20 ° C for a long time with your thumb and forefinger.
Upon release, the presence or absence of stickiness accompanied by stringing was confirmed. (3) Kowabari 60 ordinary 400-denier polyethylene net string
And then dried at 20 ° C. for 24 hours.
One of them was fixed and bent 90 °, and the return was confirmed. 2
No backlash within 2 seconds, 2 to 3 seconds, 3 seconds
The above was regarded as having cracks.

[0028]

[Table 1]

[0029]

[Table 2]

Examples 9 to 24 Each coating composition was prepared and evaluated in the same manner as in Examples 1 to 8, except that the components shown in Table 3 were used. The antifouling test was evaluated according to the following. The results are shown in Table 3.
In Table 3, “Cu ₂ O / Bioside” indicates the solid content ratio of cuprous oxide / the amount of the combined drug (other antifouling agent). The types of concomitant drugs are shown in Table 3.

(4) Antifouling property After coating and dipping in a usual manner and drying at 20 ° C. for 24 hours, a test net is set about 60 cm below the sea surface in Sukumo City, Kochi Prefecture.
Monthly antifouling property evaluation was performed. Vs. barnacles: effects on barnacles, vs. others: effects on algae, kansetsu kanashi, and smelt. Bio adhesion area; none ◎, 5% or less ○, 5-10% ○-
Δ, 10 to 20% Δ, 20% or more ×.

[0032]

[Table 3]

When applied to fishing nets, the coating compositions of Examples 1 to 8 had good adhesion and were free from tackiness and cracks. Comparative Example 1 using an acrylic resin having a high Tg, Comparative Example 2 using an acrylic resin having a low weight-average molecular weight, Comparative Examples 3, 5, and 7 not including a silicone oil, and a comparison including a small amount of an acrylic resin Example 4 and Comparative Example 6 in which the amount of the silicone oil was too small were all inferior in adhesion to the net, tackiness and / or burrs. Further, Examples 9 to 12 in which copper pyrithione and cuprous oxide were used in combination in a specific composition and polyether-modified silicone oil was used showed extremely excellent antifouling properties.

[0034]

Since the coating composition of the present invention has the above-mentioned constitution, when applied to a fishing net or the like, the coating composition has less burrs and is excellent in installation workability, has excellent adhesion to the fishing net, and has good protection by peeling off the coating film. It is possible to obtain a fishing net with little decrease in fouling.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) A01N 43/40 101 A01N 43/40 101L 59/20 59/20 Z C09D 5/16 C09D 5/16 183 / 04 183/04 (72) Inventor Hiroko Sagawa 1-26 Komagabayashi Minami-cho, Nagata-ku, Kobe Japan Paint Marine Co., Ltd. F-term (reference) 2B106 AA21 HA16 HC03 4H011 AA02 AD01 BA01 BA06 BB09 BB18 BC01 BC19 DA17 DD07 DH02 DH07 4J038 CG141 CG151 CH031 CH041 CH071 CH081 CH121 CH141 DL032 HA216 JC38 KA02 MA13 MA14 NA05 PB02 PB05 PB07 PC10

Claims (5)

[Claims] 1. A coating composition comprising an acrylic resin (A), cuprous oxide (B) and silicone oil (C),
The acrylic resin (A) has a weight average molecular weight of 50,000 or more, a glass transition temperature of -10 ° C or less, and the cuprous oxide (B) has a mass ratio to the resin solid content in the coating composition. , [Resin] / [cuprous oxide (B)] = 40 / 60-
The silicone oil (C) has a mass ratio of [resin] / [silicone oil (C)] to the resin solid content in the coating composition.
= 99/1 to 70/30. A coating composition characterized by being blended in the range of 99/1 to 70/30. 2. The composition according to claim 1, further comprising an organic antifouling agent, wherein the mass ratio of the organic antifouling agent to cuprous oxide (B) is [cuprous oxide (B)] / [organic antifouling agent. Antifouling agent] = 70 /
The coating composition according to claim 1, which is blended in the range of 30 to 98/2. 3. The organic antifouling agent is copper pyrithione, and the mass ratio of the copper pyrithione to cuprous oxide (B) is [cuprous oxide (B)] / [copper pyrithione] = 85 /
3. The coating composition according to claim 2, which is blended within a range of 15 to 95/5. 4. The coating composition according to claim 1, wherein the silicone oil (C) is a polyether-modified silicone oil. 5. The coating composition according to claim 1, which is used for an antifouling paint for fishing nets.