KR20140120675A

KR20140120675A - Colloid silica binder for antifouling paint, method for manufacturing the same and antifouling paint composition containing the same

Info

Publication number: KR20140120675A
Application number: KR1020130036824A
Authority: KR
Inventors: 이윤수; 남태구; 김웅기; 이현동
Original assignee: 주식회사 케이씨씨
Priority date: 2013-04-04
Filing date: 2013-04-04
Publication date: 2014-10-14

Abstract

The present invention relates to a colloidal silica binder for an antifouling paint, a process for producing the colloidal silica binder, and an antifouling coating composition containing the same. More particularly, the present invention relates to an antifouling coating composition comprising a top coat of a paint applied to a hull outside and an underwater structure The present invention relates to a colloidal silica binder for an environmentally friendly antifouling paint, which is applied to prevent adhesion and growth of marine life, a method for producing the same, and an antifouling paint composition containing the same.
The present invention can exhibit a bottom friction type (Foul Release Type) property by controlling the physical properties of the silicon material itself and the hydrophilicity control using an allyl polyether-modified silicon chloride intermediate, such as low surface energy of the coating film, elasticity, have. Thus, it is possible to show a basic antifouling property to marine life. Furthermore, application of an alkoxy diurethane polysiloxane intermediate makes it possible to hydrolyze by seawater, which can compensate for the long-term antifouling property which is a disadvantage of conventional silicone antifouling paints. In addition, the antifouling paint composition according to the present invention does not contain copper oxide and other organic antifouling agents and can be used as an environmentally friendly antifouling paint composition.

Description

Technical Field [0001] The present invention relates to a colloidal silica binder for an antifouling paint, a method for producing the same, and an antifouling paint composition containing the same. BACKGROUND ART [0002]

The present invention relates to a colloidal silica binder for an antifouling paint, a process for producing the colloidal silica binder, and an antifouling coating composition containing the same. More particularly, the present invention relates to an antifouling coating composition comprising a top coat of a paint applied to a hull outside and an underwater structure The present invention relates to a colloidal silica binder for an environmentally friendly antifouling paint, which is applied to prevent adhesion and growth of marine life, a method for producing the same, and an antifouling paint composition containing the same.

The antifouling paint composition is intended to prevent or control the attachment and growth of marine organisms causing surface contamination of the seawater-deposited coating film. When various marine organisms are attached to the surface of the film, the frictional force between the surface of the coating and the seawater during operation increases, which can significantly increase the fuel cost, which accounts for a large part of the operating expense.

U.S. Patent No. 3,167,473 and British Patent No. 1,475,590 disclose that a copolymer composed of a monomer in which tributyl tin is bonded to an unsaturated carboxylic acid in a salt form and a known acrylic unsaturated monomer is added to an antifouling agent and a pigment component By weight of an antifouling paint composition. The copolymer has good antifouling performance and uniform wear performance, but has been subject to regulation due to the biological problem of tin-based compounds eluted during hydrolysis. In 2003, according to the tin-free antifouling treaty, free antifouling paints have been launched.

International Patent No. 91-1554 and U.S. Patent No. 5,199,977 disclose a technique for introducing non-volatile amines, alcohols, urea and phenol compounds as ligands in order to stabilize and lower the viscosity of the metal ester-containing binder structure . Examples of the amines to be used herein include rosin amines having 12 to 20 carbon atoms. When amine is applied as a ligand, the initial rate of wear can be controlled and the metal can be stabilized and lowered in concentration to the metal. However, these amines have a lower solubility in water than binders, resulting in a rapid decrease in the wear rate of the binder over time. Ligands such as phenol, urea, and alcohol are relatively poor in water resistance, which may cause film swelling, flaking, and discoloration.

Japanese Patent No. 2-196869 discloses a hydrolyzable copolymer composed of trimethylsilyl (meth) acrylate and a known unsaturated monomer. However, trimethylsilyl (meth) acrylate has been reported to have a degree of hydrolysis of about 70% as compared with conventional tin-based binders. This indicates that the hydrolysis degree of the salt in the metal ester structure is stronger than that of tin, It is judged that it is because it falls. Therefore, the content of hydrolyzed trimethylsilyl (meth) acrylate must be higher than that of other antifouling coating compositions. The trimethylsilyl (meth) acrylate monomer is relatively expensive in terms of cost. When the content is higher than necessary, the crack resistance of the binder becomes poor. When the low molecular weight silicon monomer is applied to improve the hydrolysis property, .

Korean Patent No. 97-700680 discloses a method of mixing a plastic (meth) acrylate copolymer in order to solve the problem of a copolymer composed of the trimethylsilyl (meth) acrylate monomer. However, in this case, There is a problem in that the abrasion rate gradually decreases as the non-hydrolyzable binder remains.

Particularly, since most of the above-mentioned coating compositions contain copper oxide, which is highly environmentally harmful, as an antifouling agent, there is a tendency that a substitute product is technically studied in terms of environmental friendliness. In the case of an antifouling paint containing no copper oxide, since a relatively soft coating film is formed, the abrasion rate in an aqueous alkaline solution such as seawater is remarkably accelerated, and it is difficult to maintain the coating film in the long term, and the discoloration due to rainwater or seawater Which can lead to problems during shipbuilding and navigation.

In addition, FRC (foul release copolymer) type antifouling coating which does not contain copper oxide has excellent antifouling property due to silicon surface characteristics, but the siloxane structure starts to be partially decomposed due to ultraviolet ray, seawater condition, pH change and time elapse, Coating film imbalance and initial silicon surface properties have been changed to exhibit a long-term antifouling property.

U.S. Patent No. 3,167,473 British Patent No. 1,475,590 International Patent No. 91-1554 U.S. Patent No. 5,199,977 Japanese Patent No. 2-196869 Korean Patent No. 97-700680

In order to solve the problems of conventional antifouling paint compositions, the present invention provides a colloidal silica binder for an environmentally friendly antifouling paint capable of exhibiting excellent antifouling properties over a long period of time without containing antioxidants including copper oxide, A composition for an antifouling paint is provided.

A method for producing a colloidal silica binder for an antifouling paint according to an embodiment of the present invention comprises the steps of: (1) preparing allyl polyether-modified silicon chloride intermediate by reacting allyl ether with trichlorosilane; A second step of reacting silicon containing an isocyanate functional group with silicone containing a hydroxy functional group to prepare an alkoxy diurethane polysiloxane intermediate; And condensation polymerization of the first stage intermediate, the second stage intermediate and the colloidal silica.

The allyl polyether-modified silicon chloride intermediate may be represented by the following formula (1).

The alkoxydiurethane polysiloxane intermediate may be represented by the following formula (2).

A colloidal silica binder for an antifouling paint according to an embodiment of the present invention comprises the following components.

(a1) 10 to 40% by weight of colloidal silica;

(a2) 10 to 40% by weight of an allyl polyether-modified silicon chloride intermediate represented by the following formula (1); And

(a3) 10 to 40% by weight of an alkoxy diurethane polysiloxane intermediate represented by the following formula (2)

[Chemical Formula 1]

In Formula 1,

R1 is Cl,

R2 is _{- (C 2 H 4 O)} n -CH (n is any integer of 6 to 32) or _{- [(C 2 H 4 O} ) m - (C 3 H 6 O) n] -C 4 H 9 (m is an integer of 1 to 53, and n is an integer of 1 to 40).

(2)

In Formula 2,

And R3 is -CH _3,

R4 is -O-CH ₃ Or -OC ₂ H ₅ Lt;

and n is an arbitrary integer of 6 to 300.

The colloidal silica binder for the antifouling paint can be produced by the condensation reaction of the components including (a1), (a2) and (a3).

Wherein the colloidal silica binder for the antifouling paint comprises 3 to 15% by weight of alkoxysilanes; 1 to 8% by weight of a hydroxyl-containing polysiloxane; 1 to 8% by weight of chlorinated silanes; 1 to 8% by weight of water; And 10 to 40% by weight of a solvent.

In this specification, the colloidal silica binder for the antifouling paint can be used in the same meaning as the urethane-modified hydrophilic colloidal silica binder.

The colloidal silica binder for the antifouling paint is characterized by a surface property by a silicone component and a low friction type (Foul Release Type) property by controlling the hydrophilicity of the allyl polyether-modified silicon chloride intermediate represented by the formula (1) Can exhibit basic antifouling properties. The alkoxydiurethane polysiloxane intermediate represented by the general formula (2) is hydrolyzed by seawater to simultaneously possess magnetic abrasion properties such as general metal type acrylic antifouling resin, which is a disadvantage of a bottom-type antifouling paint Long-term antifouling property can be ensured and long-term antifouling property can be ensured without using a toxic antifouling agent such as copper oxide.

The number average molecular weight (Mn) of the colloidal silica binder for an antifouling paint measured by gel permeation chromatography (GPC) is preferably 1,000 to 20,000. In general, when the number average molecular weight of the colloidal silica binder is less than 1,000, the viscosity of the binder is too low, which makes it difficult to prepare the coating composition, and the hardness and film-forming property of the formed antifouling paint film tends to be lowered. In addition, the low molecular weight of the binder can weaken the stress between the particles inside the coating film, which can lead to cracking of the coating film and discoloration due to moisture when exposed to seawater for a long time.

When the number average molecular weight exceeds 20,000, the storage stability of the binder is lowered and further reaction by an unreacted reactor proceeds to gel. In addition, the viscosity of the binder is so high that when applied to a coating composition, the workability is lowered, and in the case of an antifouling coating film, the hydrolysis reaction of the surface tends to proceed unevenly. Therefore, the molecular weight of the binder is one of important factors influencing the viscosity and wear performance of the binder constituting the antifouling paint composition.

The colloidal silica binder for an antifouling paint according to one embodiment of the present invention can be produced by the condensation reaction of the constituents including (a1), (a2) and (a3). The antifouling paint composition according to one embodiment of the present invention is characterized by using the above-mentioned binder, and does not contain copper oxide and an organic antifouling agent.

( a1 ) Colloidal silica (10 to 40% by weight)

The silica used in one embodiment of the present invention may be a solvent-dispersed colloidal silica dispersed in a hydrophilic solvent rather than an aqueous solution. The average particle size is in the range of 10 to 100 nm. Examples of the dispersing agent include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), PMA, methoxy propanol, xylene, toluene, ethyl acetate, butyl acetate, , Isopropanol and the like can be used, but these examples do not limit the scope of the present invention.

The content of the solvent-dispersed colloidal silica may be 10 to 40% by weight, more preferably 20 to 30% by weight, based on the total weight of the colloidal silica binder for the antifouling paint.

When the amount is less than 10% by weight, the flexibility of the coating film is improved due to an increase in the relative alkoxy or chlorosiloxane intermediate component, but the strength or the degree of the coating film tends to decrease. If it is used in an amount exceeding 40% by weight, the strength of the coating film is increased but the flexibility is lowered and compatibility of the resultant binder and other organic solvents may be lowered.

( a2 ) Ally Polyether Modified silicon chloride intermediate component (10 to 40% by weight)

The allyl polyether-modified silicon chloride intermediate represented by the following formula (1) can be prepared by subjecting an allyl ether monomer containing a double bond and a trichlorosilane to a hydrolysis reaction at about 60 to 100 캜 in the presence of a platinum catalyst. Wherein the allyl ether monomer includes methoxy-polyethylene-glycol allylether having an average molecular weight in the range of 350 to 1500 and butoxy-polyethylene glycol-polypropylene glycol allylether having an average molecular weight in the range of 1600 to 2500 (Butoxy-polyethyleneglycol-polypropylene-glycol allylether), and the like are not to be construed as limiting the scope of the present invention.

[Chemical Formula 1]

In Formula 1,

R1 is Cl,

R2 is _{- (C 2 H 4 O)} n -CH 3 (n is any integer of 6 to 32), or - a _{- [(C 2 H 4 O} ) m (C 3 H 6 O) n] -C 4 H 9 (m is 1 to 53, n is 1 to 40 Lt; / RTI >

The content of the allyl polyether-modified silicon chloride intermediate component may be 10 to 40% by weight, more preferably 20 to 30% by weight, based on the total weight of the colloidal silica binder for the antifouling paint. If the content of the allyl polyether-modified silicon chloride intermediate component is less than 10% by weight, the hydrophilicity / hydrophobicity ratio of the allyl polyether-modified silicon chloride intermediate may be lowered to lower the initial antifouling property to marine life. In addition, when the content is more than 40% by weight, relatively hydrophilic / hydrophobic ratios are increased to improve initial antifouling property, but workability may be deteriorated due to poor compatibility in the coating.

( a3 ) Alkoxy Diurethane Polysiloxane The intermediate (5 to 30% by weight)

The alkoxy diurethane polysiloxane intermediate represented by formula (2) is condensed in the final hydrophilic silica binder to exhibit magnetic wear performance. Urethane functionalized silicon-urethane functional groups follow the mechanism of hydrolysis and self-abrasion of the silicon-oxygen moiety by reaction with seawater. The intermediate may be prepared by using silicon containing an isocyanate functional group and silicon containing a hydroxy functional group.

Examples of the silicon containing the isocyanate functional group include 3-isocyanate-propyl-triethoxysilane and 3-isocyanate-propyl-trimethoxysilane. can do. As the silicon containing the hydroxy functional group, di-functional or mono-functional silicon having a viscosity of 30 to 2000 cps may be exemplified. However, examples of the silicon containing the isocyanate and the hydroxy functional group do not limit the scope of the present invention.

(2)

In Formula 2,

R3 is -CH ₃ ego,

R4 is -O-CH ₃ or -OC ₂ H ₅ Lt;

and n is an arbitrary integer of 6 to 300.

The content of the alkoxydiurethane polysiloxane intermediate component may be 5 to 30% by weight, and more preferably 10 to 20% by weight based on the total weight of the colloidal silica binder for the antifouling paint. When the content of the alkoxydiurethane polysiloxane intermediate component is less than 5% by weight, the abrasion rate of the coating film becomes unbalanced with time and is low, so that the antifouling property may be lowered. In addition, when it is used in an amount exceeding 30% by weight, the viscosity of the binder and the paint becomes high, and workability can be reduced.

The above-mentioned colloidal silica binder may further contain a plurality of raw materials including general alkoxysilanes, hydroxyl group polysiloxanes, chlorinated silanes, water and a solvent in addition to the above (a1), (a2) and (a3) Condensation reaction.

The content of the alkoxysilane may be 3 to 15% by weight, more preferably 5 to 10% by weight based on the total weight of the colloidal silica binder for the antifouling paint. When the amount of the alkoxysilanes is less than 3% by weight, the alkoxy reaction ratio may be lowered during the condensation reaction of the colloidal silica binder for the antifouling paint, so that the reaction time may be increased or the conversion of the binder may be lowered. The speed is fast, but the molecular weight of the final binder to be produced is small, so that the paint viscosity may be lowered and the water resistance may be deteriorated. Examples of the alkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyltriethoxysilane (3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl triethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- methacryloxypropyl methyldiethoxysilane, 3-acryloxypropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like are used. But is not limited thereto.

The content of the hydroxyl group-containing polysiloxane component may be 1 to 8 wt%, more preferably 2 to 6 wt%, based on the total weight of the colloidal silica binder for the antifouling paint. When the amount of the hydroxyl group-containing polysiloxane component is less than 1% by weight, the strength of the coating film is improved but the flexibility may be lowered. If it is used in an amount exceeding 8% by weight, the flexibility of the coating film may increase, but the compatibility of the coating material and the storage stability may deteriorate. HEO35, HEO40, HEO60, HEP-5K, HEP-10K, HEP-20K and HEP-80K (trade name, KCC) having a number average molecular weight of 500 to 200,000 may be used as the hydroxyl group polysiloxane.

The content of the chlorinated silane components may be 1 to 8% by weight based on the total weight of the colloidal silica binder for the antifouling paint. More preferably 2 to 6% by weight. When the content of the chlorosilanes is less than 1% by weight, the improvement of the molecular weight due to the condensation reaction is limited. When the amount exceeds 8% by weight, the amount of produced by-products increases, . The chlorosilanes may be SiHCl ₃ , SiCl _4, or the like, but the present invention is not limited thereto.

The water content may be 1 to 8% by weight based on the total weight of the colloidal silica binder for the antifouling paint, more preferably 2 to 6% by weight. When the water content is less than 1% by weight, the molecular weight of the colloidal binder for the antifouling paint is also limited by the condensation reaction. When the water content is more than 8% by weight, the molecular weight of the colloid binder increases sharply, Viscosity and workability may be deteriorated and heat storage stability tends to be poor when a paint using the same is prepared.

Examples of the solvent include aromatic hydrocarbons such as xylene and toluene, aliphatic hydrocarbons such as hexane and heptane, esters such as ethyl acetate and butyl acetate and ketones such as methyl ethyl ketone and methyl isobutyl ketone. And one or more of these solvents may be used in combination. The solvent may be used in an amount of 10 to 40% by weight, more preferably 20 to 30% by weight, based on the total weight of the colloidal silica binder for the antifouling paint. When the content of the solvent is less than 10%, the solid content of the paint increases and the flowability can be improved. However, the viscosity is high and the workability is deteriorated. When the content is more than 40% by weight, All can be degraded and the solids content can be lowered.

According to one embodiment of the present invention, an antifouling paint composition comprising the above-mentioned colloidal silica binder for an antifouling paint can be provided.

The content of the silica binder for the antifouling paint may be 50 to 80% by weight, and more preferably 60 to 70% by weight, based on the total weight of the antifouling paint composition. If the content of the silica binder for the antifouling paint is less than 50% by weight, the dry film may be unevenly formed due to the reduction of the binder function due to the lack of the binder component in the pigment and the like, and the resulting hardness and water resistance may be deteriorated. If it is used in an amount exceeding 80% by weight, miscibility may be deteriorated and high temperature stability and workability may be deteriorated.

The antifouling paint composition may further comprise (a) a colloidal silica binder for an antifouling paint, (b) a pigment, (c) an additive, and (d) a solvent.

(b) zinc oxide, which acts as a pigment to improve the film strength, control the wear rate and coloring, and the like can be used. In addition, various organic and inorganic pigments known in the art can be used. Examples of the color pigments include titanium pigments such as titanium white, red iron oxide, organic red pigment, carbon black, phthalocyanine blue, titanium white, iron oxide red, iron oxide powder and chalk, zincification (ZnO, zinc oxide) White lead, red lead, and the like may be used, but the present invention is not limited thereto. Examples of the extender pigment include talc, silica, mica, clay, calcium carbonate, kaolin, magnesium carbonate, barium carbonate, barium sulfate, and bentonite used as an anti-settling agent. One or more of these may be used in combination. It is not.

(c) Various additives such as an antisagging agent, an anti-settling agent, a plasticizer such as paraffin chloride, an acrylic resin, and a polyalkyl vinyl ether (vinyl ether (co) polymer) contributing to improving the crack resistance of the antifouling coating film as additives A resin, a defoaming agent, a thickening agent (organic clay-based aluminum, calcium stearate salt of zinc, salts of lecithin salt, alkyl sulfonate and the like, polyethylene wax, amide wax, castor wax, polyamide wax, Oxidized polyethylene wax, etc.), rosin or rosin derivatives for controlling the abrasion behavior of the antifouling coating film, and the like.

(d) solvents such as aromatic hydrocarbons such as xylene and toluene, aliphatic hydrocarbons such as hexane and heptane, esters such as ethyl acetate and butyl acetate and ketones such as methyl ethyl ketone and methyl isobutyl ketone, Ethers, and alcohols can be used, and one or more of the solvents can be used in combination. In addition, various solvents generally used in antifouling paint compositions may be added.

The antifouling paint composition comprises 50 to 80% by weight of a colloidal silica binder for an antifouling paint based on the total weight of the antifouling paint composition; (b) 5 to 25% by weight of a pigment component; (c) 5 to 25% by weight of an additive component; And (d) 10 to 30% by weight of the volatile solvent component. When the content of the pigment is less than 5% by weight or exceeds 25% by weight, the color hiding power of the antifouling paint lowers or the physical properties such as the film strength deteriorate. When the additive component is less than 5% by weight or exceeds 25% If the content of the volatile solvent is less than 10% by weight or exceeds 30% by weight, the viscosity and SVR of the antifouling paint may be low or exceeded, resulting in poor workability and flowability.

The pigment may be a color and extender pigment.

The total amount of the components (a), (b), (c) and (d) may be 100% by weight.

The present invention can exhibit a bottom friction type (Foul Release Type) property by controlling the physical properties of the silicon material itself such as low surface energy, elasticity, and slippery surface of the coating film and the hydrophilic property using the allyl polyether- have. Therefore, it can exhibit antifouling property to marine life. Furthermore, application of an alkoxy diurethane polysiloxane intermediate makes it possible to hydrolyze by seawater, which can compensate for the long-term antifouling property which is a disadvantage of conventional silicone antifouling paints. In addition, the antifouling paint composition according to the present invention does not contain copper oxide and other organic antifouling agents and can be used as an environmentally friendly antifouling paint composition.

Hereinafter, the present invention will be described in more detail with reference to Examples. The objects, features and advantages of the present invention will be readily understood by the following examples. The present invention is not limited to the embodiments described herein but may be embodied in other forms. The embodiments disclosed herein are provided so that the disclosure may be thorough and complete, and that those skilled in the art will be able to convey the spirit of the invention to those skilled in the art. Therefore, the present invention should not be limited by the following examples.

Example 1 Production of colloidal silica binder for antifouling paint

(a2) Production of allyl polyether-modified silicon chloride intermediate

Allyl ether, trichlorosilane and a small amount of platinum catalyst, which are silicon monomers having an allyl functional group and an active hydrogen, are reacted in a reaction vessel equipped with a mechanical stirrer, a condenser, a thermocouple and a heating mantle , And maintained at isothermal temperature of about 85 DEG C while heating and stirring. The isothermal reaction was maintained for 5 hours under the above temperature conditions. After being maintained for 5 hours, it was cooled to prepare an allyl polyether-modified silicon chloride intermediate. The solids content of the prepared allyl polyether-modified chlorinated silicon intermediate was about 99-99.5% (calculated as the weight of the residue after drying in an oven at 150 ° C for 15 minutes). Several examples of the production of allyl polyether-modified silicon chloride intermediates Are shown in Table 1. The reaction process conditions were the same as above.

Production of allyl polyether-modified silicon chloride intermediate (unit:% by weight) division Intermediate 1 Intermediate 2 Intermediate 3 Raw material PKA5006 72.1 - 36.1 PKA5009 - 80.2 40.1 Cl ₃ SiH 27.85 19.75 23.75 Pt. cat. 0.05 0.05 0.05 Properties NV (150 DEG C * 15 min) 99.5 99.4 99.5 Viscosity (cps, # 1, 100 rpm) 28 30 30

The following ingredients were used in the ingredients used in the formulation shown in Table 1 below.

-UNIOX-PKA5006 (allyl ether, methoxy-polyethylene glycol-allyl isocyanurate, NOF)

-UNIOX-PKA5009 (allyl ether, methoxy-polyethylene glycol-allyl isocyanurate, NOF)

-Cl ₃ SiH (trichlorosilane)

(a3) Production of alkoxydiurethane polysiloxane intermediate

The silicone raw material containing the organic solvent component xylene or the hydrophilic solvent and the hydroxy functional group was put into a reaction flask equipped with a stirrer, a condenser, a thermometer, a dropping device and a heating jacket, and the temperature was raised to maintain the temperature at about 80 degrees. The alkoxysilane containing an isocyanate functional group mixed in a certain amount of the organic solvent component at the above temperature was dropped for 3 hours and then maintained at the same temperature for 5 hours. After the reaction was maintained, the reactor was cooled to prepare an alkoxy polysiloxane intermediate containing a diurethane functional group. The solid content of the alkoxydiurethane polysiloxane intermediate prepared was 70% by weight, and some examples of the preparation of the intermediate are shown in Table 2 below.

Preparation of alkoxy diurethane polysiloxane intermediate (unit:% by weight) division Intermediate 4 Intermediate 5 Intermediate 6 Raw material HEP-5K 56.1 - 28.1 HEO-60 - 36.8 18.4 KBE-9007 13.9 33.2 23.5 Xylene 30 30 30 Properties NV (150 DEG C * 15 min) 70.1 69.9 69.9 Viscosity (cps, # 1, 100 rpm) 880 560 750

The following products were used for the components used in the formulation composition shown in Table 2 above.

-HEP-5K (OH polymer, KCC)

-HEO-60 (OH polymer, KCC)

-KBE-9007 (isocyanate alkoxysilane, Shinetsu)

Manufacture of Colloidal Silica Binder for Antifouling Paint

(A1) solvent-dispersed colloidal silica (Nippon Oil) was added to a reaction flask equipped with a stirrer, a condenser, a thermometer, a dropping device and a heating jacket, and stirred for about 10 minutes. Then, the alkoxydiurethane polysiloxane intermediate (a3) prepared above, tetramethoxysilane and glycidyl silane were added dropwise over about 10 minutes and uniformly stirred. After a lapse of 10 minutes while maintaining the temperature of the reactor below 20 ° C, a certain amount of water was dropped for 30 minutes and maintained at 20 ° C or less for 30 minutes. Dropping the silicone causes the reaction to become opaque, and after about 30 minutes the reactant becomes transparent again. Then, a specific content of the allyl polyether-modified silicon chloride intermediate, CH ₃ SiCl ₃ and HEO 60 (a2) was added dropwise over about 1 hour, and the temperature was gradually raised to 85 캜 for 3 hours. At this time, the by-products resulting from the condensation were removed through a condenser and maintained at the same temperature for about 5 hours to prepare a binder. The solid content of the final binder thus prepared was 60% by weight, and examples thereof are shown in Table 3 below.

Preparation of colloidal silica binder for antifouling paint (unit: wt%) division Example 1-1 Examples 1-2 Example 1-3 Examples 1-4 Examples 1-5 Examples 1-6 won
Ryo MEK-ST 22 0 0 0 22 22 PMA-ST 0 22 22 22 0 0 Intermediate 1 18 18 0 0 0 0 Intermediate 2 0 0 18 18 18 0 Intermediate 3 0 0 0 0 0 18 Intermediate 4 15 15 15 0 0 0 Intermediate 5 0 0 0 15 15 0 Intermediate 6 0 0 0 0 0 15 Glycidylsilane
(KBM403) 5 5 5 5 5 5 Tetramethoxysilane
(MS51) 2 2 2 2 2 2 HEO60 4 4 4 4 4 4 CH ₃ SiCl ₃ 4 4 4 4 4 4 H ₂ O 4 4 4 4 4 4 Xylene 26 26 26 26 26 26 Total 100.0 100.0 100.0 100.0 100.0 100.0 water
castle NV
(150 DEG C * 15 min) 50 50 50 50 50 50 Viscosity
(cps, # 1, 100 rpm) 720 755 732 691 684 687

The following products were used for each component used in the formulation composition shown in Table 3 above.

-MEK-ST (MEK solvent-dispersed colloidal silica, Japan KK)

-PMA-ST (PMA solvent-dispersed colloidal silica, Japan KK)

-HEO60 (OH polymer, KCC)

Example 2 Preparation of antifouling paint composition

Using the thus prepared (a) colloidal silica binder for an antifouling paint, an eco-friendly non-toxic antifouling paint composition was prepared as shown in Table 4 below.

Preparation of antifouling paint composition (unit: wt%) division Example 2-1 Example 2-2 Example 2-3 Examples 2-4 Example 2-5 Examples 2-6 won
Ryo
bar
sign
more
Example 1-1 60 - - - - - Examples 1-2 - 60 - - - - Example 1-3 - - 60 - - - Examples 1-4 - - - 60 - - Examples 1-5 - - - - 60 - Examples 1-6 - - - - - 60 Red pigment 5 5 5 5 5 5 Bengala - 5 - - 5 - Titanium bag 10 5 10 10 5 10 Plasticizer 5 5 5 5 5 5 Amide wax 5 5 5 5 5 5 Xylene 15 15 15 15 15 15 Total 100.0 100.0 100.0 100.0 100.0 100.0 water
castle NV 50 50 50 50 50 50 Viscosity (KU) 91 93 93 87 88 89

The following products were used for the components used in the formulation composition shown in Table 4 below.

- Plasticizer: Paraffin plastoil 152 [Handy chemical corporation]

- Bengala (pigment): Iron Oxide Red 308 [Woo shin pigment co., Ltd.]

- TITAN BAG (PIGMENT): TIPAQUE CR-9 [Ishihara Sangyo Kaisha, Ltd.]

-Amide wax (additive): Monoral 5500M [HS Chem.]

- xylene (solvent): Xylene [SK corporation]

Comparative Example

A general purpose metal type antifouling paint A / F795 of KCC (KCC) was used as a comparative example. A / F795 is a self-polishing product with copper oxide and organic antifoulant.

The properties of the coating film, the antifouling performance and the abrasion speed of the environmentally friendly non-toxic antifouling paint composition were evaluated by the following methods.

Since this product has no similar product group, we conducted a comparison test with our general purpose metal type antifouling paint A / F795.

Experimental Example 1 Crack resistance test

An anti-corrosive coat was coated to a thickness of 150 占 퐉 on a sandblasted steel sheet having a size of 100 占 300 占 1.5 (mm) and dried for one day at room temperature (20 占 폚) A sealer coat was applied to the surface of this coating film so as to have a thickness of 100 탆 and dried at room temperature (20 캜) for 1 day to form a coating film. Then, the antifouling paint composition prepared by the formulation shown in Table 4 was coated at 600 μm (dry film thickness) for three days at intervals of one day, and cured and dried at room temperature for one week to prepare test specimens.

Thereafter, the test specimens were immersed in natural seawater at 23 ° C for 24 hours, and then the test specimens were removed from the seawater and dried outdoors for 24 hours. This cycle was repeated 30 times. After wet-dry cycling, the sample was visually inspected and evaluated according to the following criteria.

* Test specimen grade

5: No cracks or visible defects

4: Less than 5% of the total area of test specimen.

3: 5 ~ 20% cracks of the total area of test specimen

2: 20 ~ 50% of the total area of test specimen cracked.

1: 50 ~ 70% of the total area of test specimen is cracked.

0: More than 70% of the total area of the specimen is cracked.

As a result of evaluation of the strain and crack resistance of the coating film, as shown in Table 5, the antifouling coating composition of the present patent composition kept the coating cracking performance at the same level as compared with the existing antifouling paint, The crack resistance of the steel sheet does not change greatly.

Evaluation of crack resistance in antifouling paint composition Example 2-1 Example 2-2 Example 2-3 Examples 2-4 Example 2-5 Examples 2-6 Comparative Example Crack resistance 4 4 4 4 4 4 4

Experimental Example 2 Antifouling performance test in a static state

An anticorrosive coat 200 μm, a sealer coat 100 μm and an antifouling paint composition 300 μm prepared by the formulation shown in Table 4 were applied to a steel plate having a size of 550 × 150 × 2 (mm) (Based on the dry film thickness) was continuously coated at intervals of one day and cured and dried at room temperature for one week. The specimens thus prepared were immersed at a position below 1 m in terms of sea level using a raft type test equipment installed on Ulsan Bangui Port (East Coast) and Geoje Island Offshore (South Coast). The degree of contamination of the coating film due to the attachment of marine organisms was observed for 15 months periodically every 3 months after the immersion, and the antifouling performance was evaluated according to the criteria described below, and the results are shown in Table 6.

The evaluation criteria are as follows;

5: no marine life (no pollution),

4: a state in which a thin slime layer is observed,

3: a thick slime layer is observed or the vegetable contamination area is less than 20% of the effective area of the specimen,

2: The condition that the vegetable pollution area is 20 ~ 50% of the effective area of the specimen,

1: Vegetable contamination area is 50 ~ 100% of the effective area of the specimen (X: Animal contamination occurred).

As shown in Table 6 below, the copolymer composed of the components prepared in the present invention and the antifouling paint composition prepared using the same showed excellent long-term antifouling properties. It has been found that the composition containing the component (c) composed of the appropriate components (a) and (b) and the composition containing the antifouling antifoaming agent exhibits a good antifouling performance over a long period of time. The anti-fouling performance tends to be maintained with the lapse of time in the paint having a relatively large amount of the component (I-1).

Antifouling performance evaluation of antifouling paint composition term Antifouling performance of each compound Example 2-1 Example 2-2 Example 2-3 Examples 2-4 Example 2-5 Examples 2-6 Comparative Example 3 months 5 5 5 5 5 5 5 6 months 5 5 5 5 4 5 5 9 months 5 4 4 5 4 4 5 12 months 4 4 4 4 4 4 4 15 months 4 3 4 4 3 3 4 18 months 4-3 3 3 4-3 3 3 4-3

Experimental Example 3 Evaluation of wear performance (wear rate)

An anticorrosive coat 50 占 퐉, a sealer coat 50 占 퐉, and an antifouling paint composition 100 prepared by the formulation shown in Table 4 were applied to a stainless steel plate having a size of 150 × 70 × 1 (mm) Mu m were continuously coated at intervals of one day and cured and dried at room temperature for one week. The specimens thus prepared were placed on the outside of a rotating drum having a diameter of 600 mm and a height of 300 mm and rapidly rotated at a constant speed of 25 (knots) at a constant temperature of 25 ° C, The wear rate was evaluated by measuring the change, and the results are shown in FIG.

As shown in Table 7 below, it can be seen that most of the antifouling paints of the present composition patent show similar paint film abrasion rates as those of the conventional SPC type antifouling paints.

Evaluation of wear performance of antifouling paint composition term Monthly film wear (㎛) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 month 4 5 5 4 5 5 7 2 months 4 4 3 4 5 5 6 3 months 4 4 4 3 4 5 7 4 months 5 5 5 5 6 4 6 5 months 5 4 4 3 5 5 6 6 months 4 4 3 4 4 4 6 Monthly average 4.3 4.3 4.0 3.8 4.8 4.7 6.3

Claims

Reacting allyl ether with trichlorosilane to produce an allyl polyether-modified silicon chloride intermediate;
A second step of reacting silicon containing an isocyanate functional group with silicone containing a hydroxy functional group to prepare an alkoxy diurethane polysiloxane intermediate; And
And (3) condensing and polymerizing the first stage intermediate, the second stage intermediate and the colloidal silica.

The method according to claim 1,
Wherein the allyl polyether-modified silicon chloride intermediate is represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
R1 is Cl,
R2 is _{- (C 2 H 4 O)} n -CH (n is any integer of 6 to 32) or _{- [(C 2 H 4 O} ) m - (C 3 H 6 O) n] -C 4 H 9 (m is an integer of 1 to 53, and n is an integer of 1 to 40).

The method according to claim 1,
Wherein the alkoxydiurethane polysiloxane intermediate is represented by the following formula (2).
(2)

In Formula 2,
R3 is -CH ₃ ego,
R4 is -O-CH ₃ Or -OC ₂ H ₅ Lt;
and n is an arbitrary integer of 6 to 300.

A colloidal silica binder for an antifouling paint comprising the following components:
Based on the total weight of the binder,
(a1) 10 to 40% by weight of colloidal silica;
(a2) 10 to 40% by weight of an allyl polyether-modified silicon chloride intermediate represented by the following formula (1); And
(a3) 10 to 40% by weight of an alkoxy diurethane polysiloxane intermediate represented by the following formula (2)

[Chemical Formula 1]

In Formula 1,
R1 is Cl,
R2 is _{- (C 2 H 4 O)} n -CH (n is any integer of 6 to 32) or _{- [(C 2 H 4 O} ) m - (C 3 H 6 O) n] -C 4 H 9 (m is an integer of 1 to 53, and n is an integer of 1 to 40).

(2)

The method of claim 4,
Wherein the colloidal silica binder for the antifouling paint is produced by a condensation reaction of the colloidal silica, the allyl polyether-modified silicon chloride intermediate and the alkoxy diurethane polysiloxane intermediate.

The method of claim 4,
The colloidal silica binder for the antifouling paint
Based on the total weight of the binder,
3 to 15% by weight of alkoxysilane;
1 to 8% by weight of a hydroxyl-containing polysiloxane;
1 to 8% by weight of a chlorosilane;
1 to 8% by weight of water; And
And 10 to 40% by weight of a solvent. &Lt; RTI ID = 0.0 > 11. < / RTI >

An antifouling paint composition comprising a colloidal silica binder for an antifouling paint according to any one of claims 4 to 6.

The method of claim 7,
Wherein the colloidal silica binder for the antifouling paint is contained in an amount of 50 to 80% by weight based on the total weight of the antifouling paint composition.

The method of claim 7,
The antifouling paint composition may contain,
5 to 25% by weight of pigment;
5 to 25% by weight of an additive; And
And 10 to 30% by weight of a volatile solvent.