JP2010132831A - Antifouling ship bottom paint composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifouling ship bottom paint composition free from toxicity and capable of preventing soiling due to the deposition of undersea life through a long period. <P>SOLUTION: The antifouling ship bottom paint composition includes a low substitution degree hydroxy propyl cellulose having molar substitution of 0.05-1.0. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antifouling ship bottom coating composition applied to a ship bottom surface.

  The antifouling ship bottom coating has a function of physiologically killing marine organisms by preventing a slight amount of the antifouling agent from the surface of the coating film from dissolving in the seawater, thereby preventing pollution of the ship bottom. As the antifouling agent, cuprous oxide alone or in combination with an organic tin compound is mainly used. However, interest in marine environmental pollution in recent years has increased, and in particular, the antifouling agent cuprous oxide has become a problem. It is said that if copper is ingested to some extent, it accumulates in the body and has a physiological effect. In the case of ships all over the world, the amount of copper and tin leached from the bottom paint is enormous. From the viewpoint of environmental conservation, the development of a method to prevent ship bottom contamination without including these toxic components. Has been demanded.

  In response to this problem, Japanese Patent Application Laid-Open No. 58-183762 (Patent Document 1) adds a water-absorbing polymer gel containing cuprous oxide or organic tin to the paint to reduce the toxic antifouling agent as much as possible. It is proposed to be used. However, this method cannot eliminate the release of copper and tin.

  Japanese Patent Laid-Open No. 61-174273 (Patent Document 2) proposes an antifouling paint in which a water-absorbing polymer is put in the paint so that marine organisms do not adhere due to the water-absorbing polymer being slimmed. When it swells, there was a problem that the coating film peeled off. On the other hand, Japanese Patent Application Laid-Open No. 61-250071 (Patent Document 3) discloses a method of coating a large amount of water-absorbing polymer on the entire surface. In this method, the amount of water-absorbing polymer is large and expensive, and the water-absorbed polymer becomes resistance to the progress of the ship, resulting in a new problem that the fuel efficiency of the ship becomes high.

  Further, although a technique for applying a rubber-like coating film is presented in Japanese Patent Application Laid-Open No. 61-241368 (Patent Document 4), a sufficient antifouling effect is not obtained. Japanese Patent Application Laid-Open No. 11-343427 (Patent Document) discloses a method for preventing the adhesion of marine organisms by attaching a water-soluble polymer to a painted portion and gradually dissolving the water-soluble polymer to eliminate resistance to the ship. As shown in 5), this method causes all water-soluble polymers to flow out quickly and prevents the attachment of marine organisms over a long period of time.

JP 58-183762 A JP 61-174273 A Japanese Patent Laid-Open No. 61-250071 JP 61-241368 A Japanese Patent Laid-Open No. 11-343427

  This invention is made | formed in view of the said situation, and it aims at providing the antifouling ship bottom coating composition which has little toxicity and can prevent pollution by adhesion of marine organisms over a long period of time.

As a result of intensive studies to achieve the above object, the present inventor has found that the antifouling ship bottom coating composition containing a low substituted hydroxypropyl cellulose having a substituted mole number of 0.05 to 1.0 is a low substituted hydroxypropyl cellulose. by using a coating film portion reasonably be film state of containing water, by inhibiting the attachment of marine organisms, it found that it is possible to prevent contamination due to adhesion of marine organisms over long, made the present invention It has come.

That is, the present invention provides the following antifouling ship bottom coating composition.
Claim 1:
An antifouling ship bottom coating composition comprising low-substituted hydroxypropylcellulose having a substituted mole number of 0.05 to 1.0.
Claim 2:
The antifouling ship bottom coating composition according to claim 1, further comprising a crosslinking agent and / or a water-based resin emulsion.

  The antifouling ship bottom coating composition of the present invention has low toxicity and can prevent contamination due to the adhesion of marine organisms over a long period of time.

  The antifouling ship bottom coating composition of the present invention comprises a low-substituted hydroxypropyl cellulose having a substituted mole number of 0.05 to 1.0.

  The low-substituted hydroxypropylcellulose used in the antifouling ship bottom coating composition of the present invention has a number of substituted moles of hydroxypropoxyl group per glucose ring as a unit of cellulose of 0.05 to 1.0, particularly It is preferably 0.20 to 0.80. When the number of substituted moles is less than 0.05, the low-substituted hydroxypropylcellulose does not swell, and the adhesion of marine organisms cannot be prevented due to the swelling of the swelling. On the other hand, if the number of substituted moles is higher than 1.0, it becomes water-soluble, and when it is included in the paint, it dissolves and cannot exhibit a long-term antifouling effect. Such a low-substituted hydroxypropyl cellulose absorbs several thousand times as much water as a swollen water-absorbing polymer, and does not swell, and hardly damages the coating film due to swelling. The number of moles of substitution per glucose ring is determined by determining the% substitution of hydroxypropoxyl group according to the 14th revised Japanese Pharmacopoeia method for determining low-substituted hydroxypropylcellulose and converting it.

  The weight average molecular weight of the low-substituted hydroxypropyl cellulose is not particularly limited, but is preferably 53,000 to 710,000, particularly preferably 70,500 to 531,000, as a range in which the swellability is well shown. In addition, a weight average molecular weight is calculated | required by the gel permeation chromatograph (GPC-MALLS) by a light-scattering method. The average particle size of the low-substituted hydroxypropylcellulose is not particularly limited, but is preferably 20 to 55 μm, and particularly preferably 45 to 55 μm from the viewpoint that it does not aggregate as a powder and facilitates handling. The average particle diameter can be measured by a laser diffraction method.

  Such low-substituted hydroxypropyl cellulose can be obtained by reacting alkali cellulose with propylene oxide.

  The antifouling ship bottom coating composition of the present invention can be used by dissolving or dispersing the low-substituted hydroxypropyl cellulose in water, polyethylene glycol, propylene glycol or the like. 3 to 90% by mass, particularly 5 to 70% by mass of the total solid content in the antifouling ship bottom coating composition is preferred. If the amount of the low-substituted hydroxypropyl cellulose is less than 3% by mass, there may be little effect of preventing the adhesion of marine organisms, and if it exceeds 90% by mass, the coating film may be damaged due to swelling.

  In the antifouling ship bottom coating composition of the present invention, it is preferable to further use a crosslinking agent and / or a water-based resin emulsion. The crosslinking agent and / or aqueous resin emulsion used in the present invention can be used as long as it is cured by drying after coating and becomes insoluble in seawater.

As the crosslinking agent used in the present invention, any crosslinking agent can be used as long as it reacts with a hydroxyl group remaining in the molecule of the low-substituted hydroxypropylcellulose to cause a crosslinking reaction. As such a crosslinking agent, the crosslinking agent which can react with the hydroxyl group as described in a crosslinking agent handbook (October 20, 1981, Taiseisha publication) is mentioned. Specifically, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether , Alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycidyl ether, 1,6-hexanediol, diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, cresyl glycidyl ether, C3-C15 aliphatic diglycid Ether, monoglycidyl ether, epoxy acrylate, butyl glycidyl ether acrylate, ethylene glycol diglycidyl ether acrylate, trimethylolpropane polyglycidyl ether polyacrylate, terephthalic acid diglycidyl ester acrylate, phthalic acid diglycidyl ester, spiroglycol diglycidyl ether, etc. Epoxy compounds, dialdehydes such as bisphenol A and glyoxal, formaldehyde-based crosslinking agents such as urea formaldehyde, toluidine isocyanate, dimer of 2,4-toluidine isocyanate, naphthylene-1,5-diisocyanate, o -Toluidine isocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris- (p Isocyanatophenyl) thiophosphite, polymethylene polyphenyl isocyanate, polyfunctional aromatic isocyanate, aromatic polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, block polyisocyanate Nert, xylylene diisocyanate, ether- or urethane-containing block isocyanate-containing prepolymer, polyisocyanate prepolymer, block isocyanate, polyisocyanate, two-component polyisocyanate, non-yellowing two-component polyisocyanate An isocyanate-based cross-linking agent such as narate and thermosetting polyisocyanate, and a general formula SiR ¹ R ² R ³ R ⁴ (wherein R ¹ is an alkyl group having 1 or 2 carbon atoms, an alkoxy group or an acyloxy group) The table . R ² , R ³ and R ⁴ each independently represent an alkoxy group having 1 or 2 carbon atoms or an acyloxy group. ) And the like represented by These can be used alone or in combination of two or more.

  The water-based resin emulsion used in the present invention is a commonly used water-based urethane resin emulsion, water-based acrylic resin emulsion, water-based vinyl acetate resin emulsion, water-based ethylene / vinyl acetate emulsion, water-based epoxy resin emulsion, or reactive organopolysiloxane. Examples thereof include O / W type emulsions and SBR latexes, and water-based urethane resin emulsions and reactive organopolysiloxane O / W type emulsions are particularly suitable.

  Examples of water-based urethane resin emulsions include polyethers such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol, tolylene diisocyanate, 3,3′-bistolylene-4,4′-diisocyanate, and diphenylmethane. Examples thereof include various urethane resin emulsions produced by reaction with diisocyanates such as diisocyanate, 3,3-dimethyldiphenylmethane diisocyanate, and 4,4′-diisocyanate.

  O / W type emulsions of organopolysiloxanes are described in US Pat. No. 4,221,688 and pages 248-251 of Silicone Handbook (edited by Kunio Ito, August 31, 1990, published by Nikkan Kogyo Shimbun). Methyl hydrogen polysiloxane, terminal hydroxyl-blocked dimethyl polysiloxane, vinyl group-containing polysiloxane, organopolysiloxane having at least two hydroxyl groups bonded to silicon atoms described in JP-B-3-67145, etc. And the like dispersed in the above. These may be used singly or in combination of two or more, but it is preferable to use those containing 10 to 90% by mass, particularly 40 to 80% by mass as the solid content.

  Also, various metal salts such as tin, lead, zinc, cobalt, manganese, chromium, zirconium, titanium, platinum, etc. should be used as a catalyst for promoting the crosslinking reaction with O / W emulsions of these reactive organopolysiloxanes. In particular, zirconium acetate described in JP-B No. 34-4199 and dichloroplatinic acid described in JP-B No. 51-9440 are useful. The amount of these catalysts used is not particularly limited, but as a reasonable amount for promoting the crosslinking reaction, 0.001 to 120 parts by mass with respect to 100 parts by mass of the reactive organopolysiloxane in the emulsion to be used, 0.005-110 mass parts is especially preferable. Although it does not specifically limit as a particle diameter of O / W type | mold emulsion, 0.01-100 micrometers, Especially 0.1-80 micrometers are preferable from a stability viewpoint as an emulsion.

  Although the addition amount of a crosslinking agent is not specifically limited, 5-50 mass parts with respect to 5 mass parts of low substituted hydroxypropylcellulose, especially 10-30 mass parts is preferable. The addition amount of the water-based resin emulsion is not particularly limited, but is preferably 10 to 150 parts by mass, particularly preferably 15 to 120 parts by mass with respect to 5 parts by mass of the low-substituted hydroxypropylcellulose. If there are too many crosslinking agents and / or water-based resin emulsions, it may not be possible to coat a low-substituted hydroxypropylcellulose film containing water. If too little, a low-substituted hydroxypropylcellulose film containing water on the bottom of the ship. May not be fixed and may be easily peeled off.

  Furthermore, oils such as silicone oil may be blended for the purpose of improving the gloss of the coating film within a range that does not interfere with the present invention. As the silicone oil, it is preferable to use a dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil or the like having a viscosity at 25 ° C. of about 1 to 1,000 mPa · s. In addition, the measured value of a viscosity is based on BL type rotational viscometer with the rotation speed of 30 rpm in 20 degreeC.

  As for the addition amount of silicone oil, 10-30 mass parts is preferable with respect to 20 mass parts of low substituted hydroxypropylcellulose, More preferably, it is 15-25 mass parts. If it is out of the above range, the gloss by the coating film may not be improved or the adhesion to the ship bottom may be deteriorated.

  The antifouling ship bottom coating composition of the present invention comprises a low-substituted hydroxypropyl cellulose, a cross-linking agent and / or a water-based resin emulsion, if necessary, a mixer having a vertical rotating blade such as a spiral mixer, and a double-arm kneader. It can prepare by mixing for 3 to 20 minutes at 5-30 degreeC using mixers, such as a mixer with a horizontal rotating blade, a screw mixer, a rotation homogenizer.

  The thus obtained antifouling ship bottom coating composition of the present invention is applied by a doctor blade, brush coating, spray coating or the like, and then dried at room temperature (25 ° C.) to 90 ° C. to form a coating film. be able to. The thickness of the cured coating film is preferably 10 to 400 μm, more preferably 20 to 300 μm. If it is too thick, it may be easy to peel off when the ship's bottom collides with rocks, etc. If it is too thin, it may be difficult to form a coating film containing water with a thickness necessary for marine organisms to be difficult to adhere. .

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example. In the following examples, the viscosity is measured with a BL type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.) at 20 ° C.

[Examples 1 to 4, Comparative Examples 1 and 2]
The paint material having the composition shown in Table 1 was mixed in a 200 ml beaker with a 700 rpm screw type stirring blade for 2 minutes at room temperature (25 ° C.) to prepare an antifouling ship bottom paint composition.
Prepare a polyethylene terephthalate (PET) sheet having a thickness of 100 μm as an object to be coated, coat it to a thickness of 100 μm with a doctor blade with variable thickness, and then repeat drying at room temperature (25 ° C.) to obtain a coating thickness of 0.3 mm. A painted sheet was obtained.
Cut out three sheets so that the area of the painted surface is 100 cm ² , sandwich each sheet with a metal clip, so that it does not flow with a string attached to the tip of the clip, soaked on the Naoetsu coast of Joetsu City, Niigata Prefecture The samples were left for 6 months and 12 months to observe how much barnacles adhered to the painted surface. Table 1 shows the evaluation points for each of the three sheets, with 0 to 5 points assigned to the entire surface.
<Evaluation criteria>
5 points: adhered to the entire painted surface 4 points: adhered to approximately 80% of the painted surface 3 points: adhered to approximately 60% of the painted surface 2 points: adhered to approximately 40% of the painted surface 1 point: 10 to 20 of the painted surface Adhering to about 0%: No adhesion on the painted surface

水系樹脂エマルジョン：信越化学工業（株）製 オルガノポリシロキサンのＯ／Ｗ型
エマルジョン ＫＥ−４５
シリコーンオイル：信越化学工業（株）製 ジメチルシリコーンオイル（ＫＦ９６Ｌ
−１ＣＳ） １ｍＰａ・ｓ
架橋剤：ポリエチレングリコールジグリシジルエーテル 日油（株）製 エピオール
Ｅ−１０００
低置換度ヒドロキシプロピルセルロース：信越化学工業（株）製
（１）置換モル数０．０５の低置換度ヒドロキシプロピルセルロース
重量平均分子量１０６，２００
（２）置換モル数１．０の低置換度ヒドロキシプロピルセルロース
重量平均分子量７０，８００
＊）・／・／・は、３枚各シ−トの評価結果を示す。

Water-based resin emulsion: O / W type of organopolysiloxane manufactured by Shin-Etsu Chemical Co., Ltd.
Emulsion KE-45
Silicone oil: dimethyl silicone oil (KF96L) manufactured by Shin-Etsu Chemical Co., Ltd.
-1CS) 1mPa · s
Crosslinking agent: Polyethylene glycol diglycidyl ether, NOF Corporation Epiol E-1000
Low-substituted hydroxypropyl cellulose: manufactured by Shin-Etsu Chemical Co., Ltd.
(1) Low substituted hydroxypropyl cellulose having a substituted mole number of 0.05
Weight average molecular weight 106,200
(2) Low substituted hydroxypropyl cellulose having a substituted mole number of 1.0
Weight average molecular weight 70,800
*) .///. Indicates the evaluation result of each of the three sheets.

Claims (2)

  An antifouling ship bottom coating composition comprising low-substituted hydroxypropylcellulose having a substituted mole number of 0.05 to 1.0.   The antifouling ship bottom coating composition according to claim 1, further comprising a crosslinking agent and / or a water-based resin emulsion.