KR101270522B1 - Resin composition for Antifouling paint comprising waterborne polysiloxane-urethane-urea dispersions and a antifouling films formed from the composition - Google Patents

Abstract

상기 식에서,
Ut는 우레탄기이고, Ur은 우레아기이며,
R₁ 및 R₂는 탄소수 1 내지 3의 선형 알킬기이고,
n은 1 내지 50의 정수이다.
본 발명에 따르면, 수성 폴리실록산-우레탄-우레아 분산액을 방오도료 조성물에 적용한 것으로서, 폴리실록산을 주성분을 구성하는 수성 분산액을 방오도료에 적용함으로써 별도의 방오제를 필요로 하지 않거나 사용함량을 절감시키면서도 열적 안정성, 기계적 성질, 방오성이 우수한 방오도료와 상기 방오도료를 도포하여 경화한 성형품을 제조할 수 있다.A resin composition for an antifouling paint comprising an aqueous polysiloxane-urethane-urea dispersion having a terminal group represented by the following Formula 1 is disclosed:
[Formula 1]

In this formula,
Ut is a urethane group, Ur is a urea group,
R ₁ and R ₂ are linear alkyl groups having 1 to 3 carbon atoms,
n is an integer from 1 to 50.
According to the present invention, an aqueous polysiloxane-urethane-urea dispersion is applied to an antifouling coating composition. By applying an aqueous dispersion comprising polysiloxane as a main component to an antifouling coating, thermal stability is required without requiring an additional antifouling agent or reducing the use amount. The antifouling paint having excellent mechanical properties and antifouling properties and a molded article obtained by applying the antifouling paint can be prepared.

Description

Resin composition for antifouling paint comprising waterborne polysiloxane-urethane-urea dispersions and a antifouling films formed from the composition}

The present invention relates to a resin composition for an antifouling paint comprising an aqueous polysiloxane-urethane-urea dispersion, and more particularly, to an aqueous polysiloxane-urethane- that is excellent in mechanical properties and can be used for an antifouling paint that protects a surface from marine pollution. It is related with the resin composition for antifouling paints containing a urea dispersion liquid.

Polyurethane resins are widely used as adhesives and paints because of their excellent adhesion, flexibility and mechanical strength. Such polyurethanes have been used as an organic solvent-based polyurethane in which a polyurethane resin is dissolved in an organic solvent, but the organic solvent does not necessarily have a good effect on the human body or the environment. In addition, due to the risk of ignition, the development of an aqueous polyurethane composed of a polyurethane resin aqueous dispersion in which a polyurethane resin is dispersed in water, instead of the organic solvent-based polyurethane, has been rapidly developed. have.

As an aqueous polyurethane, for example, JP-A-63 (1988) -69882 discloses an aliphatic polyisocyanate obtained by reacting an adipic acid-based polyester polyol and a polyol having a carboxylic acid group or a sulfonic acid group. A self-emulsifying aqueous polyurethane has been proposed. The process for producing an aqueous polyurethane is environmentally friendly and free of contamination. Thus, water-based polyurethanes are widely used as paints and adhesives in the automotive, construction, textile, paper and footwear industries.

However, the use of this application also caused problems of deterioration in mechanical strength, thermal stability and adhesive strength, and in order to improve this, 2,2-dimethylol propionic acid (DMPA) content, poly (tetramethylene adipate glycol), or Various attempts have been made such as including aliphatic curing agents, admixtures, and crosslinking agents. As a result of these efforts, aqueous polyurethane nanocomposites with improved thermal and mechanical stability have been prepared.

Recently, silane technology has been rapidly developed in the field of antifouling paints, and this technology is based on an environmentally safe organic-inorganic silicone-based compound that provides stable adhesion to paint as well as corrosion and microbial protection. Over the last few years, silane resins have been an attractive choice as a coating to protect surfaces from marine pollution.

Marine biofouling can occur due to undesirable accumulation of microorganisms and plants in artificial structures exposed to marine ecosystems. In particular, this phenomenon is observed in the description of the bottom, underwater structures, fishing nets, etc., which have been exposed to seawater for a long time. Protective coatings have evolved to reduce marine pollution.

As a method of preventing the adhesion of these harmful organisms, a conventional method of coating an antifouling paint has been adopted, and an organic tin compound has been mainly used as the antifouling agent in the antifouling paint. Recently, however, the use of such antifouling agents has been banned from the viewpoint of safety for the ecosystem.

However, all of the antifouling coating compositions have room for improvement in terms of antifouling properties, especially long-term antifouling properties, and in order to obtain a sufficient antifouling effect, a large amount of antifouling agents must be added. do.

In order to solve the above problems,

It is an object of the present invention to provide a resin composition for antifouling paint comprising an aqueous polysiloxane-urethane-urea dispersion which can obtain antifouling properties, thermal stability, and mechanical properties of an existing antifouling paint composition without using a separate antifouling agent. do.

In addition, to solve the above problems, the present invention

To provide an antifouling coating film formed from a resin composition for antifouling coatings including an aqueous polysiloxane-urethane-urea dispersion, which can obtain the antifouling properties, thermal stability, and mechanical properties of existing antifouling paint compositions without using a separate antifouling agent. For the purpose of

In order to achieve the above object, the present invention provides a resin composition for antifouling paint comprising an aqueous polysiloxane-urethane-urea dispersion represented by the following formula (1):

[Formula 1]

Where

Ut is a urethane group, Ur is a urea group,

R ₁ and R ₂ are linear alkyl groups having 1 to 3 carbon atoms,

n is an integer from 1 to 50.

To achieve these and other objects,

An antifouling coating film formed from a resin composition for antifouling coating comprising an aqueous polysiloxane-urethane-urea dispersion is provided.

The present invention applies an aqueous polysiloxane-urethane-urea dispersion to a resin composition for antifouling paints, and by applying an aqueous dispersion liquid comprising polyurethane as a main component to an antifouling paint, it does not require a separate antifouling agent or thermally reduce the amount of use. The antifouling coating composition of the present invention can form an antifouling coating having excellent stability, mechanical properties, and antifouling properties, and the antifouling coating film of a ship or a ship structure to which the antifouling coating is applied can prevent the leaching of the antifouling agent in seawater in advance. May be applied as an environmentally friendly antifouling paint that can reduce the pollution of the marine environment.

1 shows the FTIR spectra of an aqueous polyurethane (a) and an aqueous polysiloxane-urethane-urea (b) according to one embodiment of the invention.
2 shows a ¹ H-NMR spectrum of an aqueous polysiloxane-urethane-urea according to one embodiment of the present invention.
3 shows a ²⁹ Si-NMR spectrum of an aqueous polysiloxane-urethane-urea according to one embodiment of the present invention.
4 shows the XPS results of aqueous polyurethane (a) and aqueous polysiloxane-urethane-urea ((b)-(f)) according to one embodiment of the invention.
5 shows curve fitting results of XPS C of an aqueous polysiloxane-urethane-urea (a) and an aqueous polyurethane (b) according to an embodiment of the present invention.
6 shows AFM 3D topography of aqueous polyurethanes (a) and aqueous polysiloxane-urethane-ureas ((b)-(c)) according to one embodiment of the invention.
7 is a photograph of the surface of the sample after 1 month (a), 2 months (b), 3 months (c) after immersing the aqueous polyurethane and aqueous polysiloxane-urethane-urea in seawater according to an embodiment of the present invention Illustrated.

Hereinafter, the present invention will be described in detail.

The present invention provides a resin composition for antifouling paint, comprising an aqueous polysiloxane-urethane-urea dispersion represented by the following Chemical Formula 1:

[Formula 1]

Where

Ut is a urethane group, Ur is a urea group,

R ₁ and R ₂ are linear alkyl groups having 1 to 3 carbon atoms,

n is an integer from 1 to 50.

Although antifouling paints usually consist of polymer resins, antifouling agents, pigments, additives, and organic solvents, the antifouling paints according to the invention are characterized by being able to consist only of the aqueous polymer resins synthesized in the examples. The polymer resin of the present invention will be present in a dispersed form in water, and when such a resin is applied to the bottom, only water will surround the resin and thus will be protected from environmental pollution. In addition, it can be said that it is safe from marine pollution because it can be added or contain less antifouling agent separately.

The content of water in the aqueous polysiloxane-urethane-urea dispersion is preferably 20 to 80% by weight of the total content of the dispersion. If the water content is less than 20% by weight The hydrolysis reaction and the condensation reaction do not proceed completely in the water dispersion step, which is not preferable. When the amount exceeds 80% by weight, the solid content in the resin is lowered, which is not preferable.

The number average molecular weight (Mn) of the aqueous polysiloxane-urethane-urea according to the present invention is preferably 5,000 to 35,000. If the number average molecular weight is less than 5,000 is not preferable because the physical properties of the resin is not properly implemented, if it exceeds 35,000 it is not preferable because it is difficult to disperse the resin.

Polyols usable in the present invention are generic terms for polyhydroxy compounds having a structure obtainable by substituting hydroxyl groups for a plurality of hydrogens present on hydrocarbons. In particular, the polyol compound is the product of addition polymerization of one or more alkylene oxides (eg ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran) to a compound having two or more active hydrogens. Specific examples of the compound having two or more active hydrogens that can be used include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerol, hexanetriol, trimethylolpropane, pentaerythritol, and the like. Additionally, polyether polyols (eg polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylenediol, polyoxypropylenetriol and polyoxybutylene glycol), polyolefin polyols (eg polybutadiene Polyhydric alcohols and resorcinols, such as polyols and polyisoprene polyols), polytetramethylene oxide glycol (PTMG), polyester polyols (PES), adipate polyols, lactone polyols, polyester polyols (e.g. castor oil) and Polyhydric phenols such as bisphenols.

Preferred polyols used in the present invention are hydroxy terminated polydimethylsiloxane (PDMS) and polytetramethylene oxide glycol (PTMG). Silicon atoms in the hydroxy-terminated polydimethylsiloxane (PDMS) contribute to the formation of siloxane, and silicon (Si) atoms smooth the surface among the physical properties of the resin of the present invention to affect the adhesion of contaminants, resulting in antifouling performance. Have it. Therefore, it is possible to control the antifouling performance of the dispersion by adjusting the content of the polydimethylsiloxane (PDMS) of the hydroxy end. The content of the hydroxy-terminated polydimethylsiloxane (PDMS) is preferably 15.0 to 33.0% by weight, more preferably 15.0 to 25.0% by weight of the entire dispersion. When the content of the hydroxy-terminated polydimethylsiloxane (PDMS) is less than 15.0% by weight, the antifouling performance is insignificant, and it is not preferable. When the content of the polydimethylsiloxane (PDMS) is more than 33.0% by weight, the formation of a coating film occurs, which is not preferable. PTMG is also obtained by ring-opening polymerization of tetrahydrofuran.

In addition, the content of the total polyol used in the present invention is preferably 33.1 to 70.0% by weight. The polyol may form a soft segment upon polymer formation.

The polyisocyanate which can be used in the present invention is not particularly limited, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and the like.

Aliphatic polyisocyanates usable in the present invention include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, Aliphatic diisocyanates such as 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate and 2,6-diisocyanate methyl caproate; For example, lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6- And aliphatic triisocyanates such as triisocyanate hexane and 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane.

As the alicyclic polyisocyanate usable in the present invention, for example, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5 , 5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate Alicyclic diisocyanates such as 1,3- or 1,4-bis (isocyanate methyl) cyclohexane (common name: hydrogenated xylene diisocyanate) or mixtures thereof, norbornane diisocyanate; For example, 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2- (3-isocyanatepropyl) -2,5-di (isocyanatemethyl) -bicyclo (2.2. 1) heptane, 2- (3-isocyanatepropyl) -2,6-di (isocyanatemethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatepropyl) -2,5-di (isocyanatemethyl) -Bicyclo (2.2.1) heptane, 5- (2-isocyanateethyl) -2-isocyanatemethyl-3- (3-isocyanatepropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanate Ethyl) -2-isocyanatemethyl-3- (3-isocyanatepropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanateethyl) -2-isocyanatemethyl-2- (3-isocyanatepropyl) -ratio Alicyclic triisocyanates such as cyclo (2.2.1) -heptane and 6- (2-isocyanateethyl) -2-isocyanatemethyl-2- (3-isocyanatepropyl) -bicyclo (2.2.1) heptane; have.

As the aliphatic polyisocyanate usable in the present invention, for example, 1,3- or 1,4-xylene diisocyanate or mixtures thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3 Or aromatic aliphatic diisocyanates such as 1,4-bis (1-isocyanate-1-methylethyl) benzene (common name: tetramethylxylene diisocyanate) or mixtures thereof, for example, 1,3,5-triisocyanate methyl Aromatic aliphatic triisocyanate, such as benzene, etc. are mentioned.

Aromatic polyisocyanates usable in the present invention include, for example, m-phenylene diisocyanate, p-phenylenedi isocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'- diphenylmethane diisocyanate or mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4 'toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, etc. Aromatic diisocyanate; Aromatic triisocyanates such as triphenylmethane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanate toluene, for example, 4, Aromatic tetraisocyanates, such as 4'-diphenylmethane-2,2 ', 5,5'- tetraisocyanate, etc. These polyisocyanates can be used independently and can be used together 2 or more types. It is preferable that the content of isocyanate to be 15 to 55% by weight.

Compounds having one or more crosslinkable functional groups include carboxyl, carbonyl, amine, hydroxyl, hydrazide groups and compounds having mixtures of these groups. Preferred monomers for incorporation into isocyanate terminated prepolymers are hydroxy-carboxylic acids having the formula (HO) xQ (COOH) y, wherein Q is a straight or branched hydrocarbon radical having 1 to 12 carbon atoms, x and y are 1 to 3. Examples of such hydroxy-carboxylic acids include citric acid, dimethylolpropanoic acid (DMPA), dimethylol butanoic acid (DMBA), glycolic acid, lactic acid, malic acid, dihydroxymalic acid, tartaric acid, hydroxypivalic acid and the like and mixtures thereof. This includes. Dimethylolpropanoic acid (DMPA) is more preferred. In addition, the content of the compound having a crosslinkable functional group is preferably 5 to 15% by weight.

In the synthesis of the isocyanate terminated prepolymer, before or after the reaction, for example, amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine; For example, alkali metal hydroxides, such as potassium hydroxide and sodium hydroxide; It is preferable to add other neutralizing agents such as ammonia to neutralize the anionic groups to form salts. The content of the component used as the neutralizing agent is preferably 3 to 10% by weight.

Examples of the amine usable in the present invention include diamines such as ethylenediamine, propylenediamine, hexamethylenediamine and hydrazine; For example, trifunctional or more than trifunctional polyamine, such as diethylene triamine, triethylene tetratamine, and tetraethylene pentamine, etc. are mentioned, Ethylene diamine and propylene diamine are preferable.

As the chain extender, one or more of water, inorganic or organic polyamines having an average of at least about two primary and / or secondary amine groups, polyalcohols, ureas, or combinations thereof are suitable for use in the present invention. Suitable organic amines for use as chain extenders include diethylene triamine (DETA), ethylene diamine (EDA), meta-xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methylpentane diamine, and the like. And mixtures thereof. Preferably propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, phenylene diamine, tolylene diamine, 3,3-dichlorobenzidene, 4,4'-methylene-bis- (2-chloroaniline) , 3,3-dichloro-4,4-diamino diphenylmethane, sulfonated primary and / or secondary amines, and the like and mixtures thereof. In the present invention, the content of the chain extender is preferably 0.1 to 5% by weight.

After the completion of the reaction, when the resin is synthesized by solution polymerization, it is preferable to remove the organic solvent by heating to an appropriate temperature, for example, under reduced pressure. In order to improve the stability of the aqueous polysiloxane urethane urea dispersion of the present invention, the surfactant may be further mixed within a limit that does not adversely affect the water resistance.

The aqueous polysiloxane-urethane-urea dispersion according to the present invention may further comprise suitable solvents, pigments and additives in order to further maximize antifouling properties. In the case of forming the antifouling paint using the dispersion, the content of the solvent, the pigment, and the additive used may be optionally selected from the ranges used in the conventional antifouling coating composition.

When a specific amount of hydroxy-terminated PDMS used as a polyol is used, the coating surface is very smooth and slippery and acts as an antifouling agent, thereby significantly reducing contamination or corrosion. Therefore, it is possible to manufacture an antifouling coating composition by appropriately controlling the amount of PDMS used without the antifouling agent usually used in antifouling paints. Therefore, the aqueous polymer dispersion according to the present invention can be said to be very environmentally friendly because it can cope with marine pollution caused by the antifouling agent.

According to another aspect of the present invention, there is provided an antifouling coating film formed from the resin composition for antifouling paint containing the aqueous polysiloxane-urethane-urea dispersion.

Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

Example

matter

PTMG: Polytetramethylene oxide glycol (number average molecular weight 2,000 g / mol, purchased by Aldrich)

PDMS: Number average molecular weight 2,000 g / mol, purchased by Aldrich (Reagent name: POLY (DIMETHYLSILOXANE), HYDROXY TERMINATED (CAS-NO 70131-67-8))

TEA: triethylamine (purchased from Junsei Chemical)

NMP: N-methyl-2-pyrrolidone (purchased from Junsei Chemical)

H ₁₂ MDI: 4,4'-dicyclohexylmethane diisocyanate (by Aldrich)

EDA: Ethylenediamine (purchased from Junsei Chemical)

DMPA: 2,2-bis (hydroxymethyl) propionic acid (purchased from Junsei Chemical)

Mercury Polysiloxane  urethane Urea ( WBPSUU ) Preparation of Dispersion

Example  One - WBPSUU1

60.2 g of polyol (PTMG) was added to a four-necked flask with a thermometer, a stirrer, a condenser with a drying tube, an inlet and outlet for dry nitrogen, and a heating jacket. The gas was removed under vacuum at 90 ° C. for 30 minutes. 6.2 g of DMPA / NMP (1/1 w / w) was added to the mixture at 60 ° C. and stirred for 30 minutes. The reaction was cooled to 45 ° C. and stirred at 175-200 rpm. Then, as a catalyst dibutyltin dilaurate a drop was added (0.01% by weight, based on H ₁₂ MDI) to the flask with H ₁₂ MDI 25.5 g, while stirring the mixture was heated to 85 ℃ was reacted for 3 hours . Changes in NCO levels during the reaction were measured using standard dibutylamine back titration (ASTM D1638). Subsequently, 10 g of methyl ethyl ketone (MEK) was added to the NCO terminated prepolymer mixture at 65 ° C. to adjust the viscosity of the solution. Also 4.7 g of TEA was added to the reaction mixture at 65 ° C. to neutralize the carboxyl groups of the NCO terminated prepolymer.

After 30 minutes, 70% by weight of distilled water was added to the reaction mixture and stirred vigorously (1300-1500 rpm). The neutralized prepolymer extended the chain of neutralized prepolymer by dropping 1.0 g of EDA at 40 ° C. for 1 hour. The reaction was continued until the NCO peak (2000-2300 cm ^-1 ) disappeared completely in the IR spectrum. The dispersion was obtained after MEK evaporation.

Example  2 - WBPSUU2

Aqueous polysiloxane urethane urea dispersion ( WBPSUU2 ) was prepared in the same manner as in Example 1 except that 55.0 g of PTMG, 5.0 g of PDMS, 27.2 g of H ₁₂ MDI, 6.2 g of DMPA, 4.7 g of TEA, and 1.0 g of EDA were reacted. .

Example  3 - WBPSUU3

Aqueous polysiloxane urethane urea dispersion ( WBPSUU3 ) was prepared in the same manner as in Example 1, except that 42.3 g of PTMG, 11.6 g of PDMS, 31.4 g of H ₁₂ MDI, 7.7 g of DMPA, 5.8 g of TEA, and 1.2 g of EDA were reacted. .

Example  4 - WBPSUU4

An aqueous polysiloxane urethane urea dispersion ( WBPSUU4 ) was prepared in the same manner as in Example 1, except that 34.4 g of PTMG, 15.8 g of PDMS, 33.9 g of H ₁₂ MDI, 8.3 g of DMPA, 6.3 g of TEA, and 1.3 g of EDA were reacted. .

Example  5 - WBPSUU5

Aqueous polysiloxane urethane urea dispersion ( WBPSUU5 ) was prepared in the same manner as in Example 1, except that 25.0 g of PTMG, 20.6 g of PDMS, 37.1 g of H ₁₂ MDI, 9.1 g of DMPA, 6.8 g of TEA, and 1.7 g of EDA were reacted. .

Water based polyurethane Silane  Preparation of dispersion

Comparative example  One - WBPU

64.8 g of polyol (PTMG) was added to a four-necked flask with a thermometer, a stirrer, a condenser with a drying tube, an inlet and outlet for dry nitrogen, and a heating jacket. The gas was removed under vacuum at 90 ° C. for 30 minutes. 5.9 g of DMPA / NMP (1/1 w / w) was added to the flask and the mixture was cooled to 45 ° C. and stirred. A drop of dibutyltin dilaurate as catalyst was then added to the flask with 24.0 g of H ₁₂ MDI and the mixture was reacted for 3 hours while heating to 85 ° C. with stirring. Changes in NCO levels during the reaction were measured using standard dibutylamine back titration. Subsequently, methylethylketone (MEK, 10 wt%) was added to the NCO-terminated prepolymer mixture at 65 ° C. to adjust the viscosity of the solution. Also, 4.4 g of TEA was added to the reaction mixture at 65 ° C. to neutralize the carboxyl groups of the NCO terminated polyurethane prepolymer. After neutralizing for 30 minutes, distilled water (70% by weight) was added to the reaction mixture with vigorous stirring. The neutralized prepolymer was chain extended by 0.9 g of EDA dropped for 1 hour at 40 ° C. and the reaction continued until the NCO peak disappeared completely from the IR peak. A dispersion (30% solids component) was obtained after MEK evaporated.

In Examples 1 to 5 and Comparative Example 1, the contents of each substance added to the reaction are shown in Table 1 below.

matter Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 PTMG 60.2 55.0 42.3 34.4 25.0 64.8 PDMS 2.4 5.0 11.6 15.8 20.6 0.0 H ₁₂ MDI 25.5 27.2 31.4 33.9 37.1 24.0 DMPA 6.2 6.7 7.7 8.3 9.1 5.9 TEA 4.7 5.0 5.8 6.3 6.8 4.4 EDA 1.0 1.1 1.2 1.3 1.4 0.9 Sum 100 100 100 100 100 100

(Unit: g)

WBPSUU  And WBPU  Manufacture of film

The dispersions (10 g) of Examples 1 to 6 and Comparative Example 1 prepared beforehand were poured onto a Teflon disc having a diameter of 7 cm, and then dried under atmospheric conditions for about 48 hours to form a film. The dried film (thickness about 0.5 mm) was cured by annealing at 60 ° C. for 6 hours, followed by additional vacuum drying for 12 hours. The vacuum dried film was stored in a dryer at room temperature.

In sea water Immersion  Experiment

The synthesized aqueous resin was mounted on a flat PVC support. The film sample was completely dried within 4 hours at ambient temperature, and an immersion test was conducted using it. Immersion test was conducted in Suyeong Bay, Busan, Korea since August 2009. A sample mounted on the PVC support was immersed about 1 meter below the water surface.

Assessment Methods

The average particle diameter of the dispersion was measured using a laser scattering apparatus (Autosizer, Malvern IIC, Malvern, Worcester, UK). The structure of WBPSUU was confirmed by Fourier Transform IR spectrometer (Impact 400D, Nicolet, Madison, WI, USA). And analyzed.

¹ H NMR and ²⁹ Si NMR spectra were obtained on a JEOL C60 HL spectrometer using CDCl ₃ as solvent. Gel permeation chromatography (Model 500, Analytical Scientific Instruments, USA) was determined by molecular weight relative to polystyrene at 30 ° C. A calibration curve was obtained using eight standards in the range 3420 × 10 ⁶ to 2.57 × 10 ⁶ .

Tensile tests were measured according to ASTM D 638 using a United Data System tension meter (Instron SSTM-1, United Data System, Inc.) at room temperature. Final tensile strength, modulus and elongation at break were measured using a crosshead speed of 50 mm / min for all samples. These figures represent the mean values in five measurements.

The surface of the polymer was measured using XPS using an ESCA 250 X-ray Photoelectron Spectrometer (XPS). AFM was measured using a scanning probe microscope (SPM-Solver P47, NT-MDT, Russia).

Evaluation results

synthesis Aqueous siloxane -urethane- Urea  Confirmation of such

1 shows the FTIR spectra of an aqueous polyurethane (a) and an aqueous polysiloxane-urethane-urea (b) according to one embodiment of the invention. The FTIR spectral results in FIG. 1 confirm successful hydrolysis and condensation reactions during the preparation of aqueous polyurethanes and aqueous polysiloxane-urethane-ureas. 2 shows a ¹ H-NMR spectrum of an aqueous polysiloxane-urethane-urea according to one embodiment of the present invention. 2, the structure of the aqueous polysiloxane-urethane-urea according to the present invention can be confirmed. 3 shows a ²⁹ Si-NMR spectrum of an aqueous polysiloxane-urethane-urea according to Example 4 of the present invention. Referring to FIG. 3, only one chemical shift corresponding to the silicon atom present in Example 4 is shown.

XPS  analysis

4 shows the XPS results of aqueous polyurethane (a) and aqueous polysiloxane-urethane-urea ((b)-(f)) according to one embodiment of the invention. Referring to FIG. 4, the peaks at 531, 285, 101, and 150 eV of the aqueous polysiloxane-urethane-urea ((b) to (f)) are the spectra of oxygen, carbon, silicon (1s), and silicon (2s), respectively. To show. Peaks at 531, 285 and 400 eV are observed in the aqueous polyurethane of the comparative example. The results show that the chemical properties of the aqueous polyurethane and the aqueous polysiloxane-urethane-urea are different from each other. The hard segments of polyurethane are usually in a glazed state, and the soft segments can easily move to the surface area with high mobility. Therefore, the structure of polyurethane is very complicated and related to the number of carbon atoms and to different binding energies.

5 shows curve fitting results of XPS C of an aqueous polysiloxane-urethane-urea (a) and an aqueous polyurethane (b) according to an embodiment of the present invention. Referring to Figure 5, the polymer resin of the present invention can be separated into several constituent groups, specifically, C-Si can be confirmed at 280-283.8eV, CO can be confirmed at 289.7-285.8eV, CC Or CH can be found at 282.0-285.9 eV and CN can be found at 284.1-286.1 eV and 284.5-287.1 eV, respectively. The relative area of each group is shown in Table 3 below.

number C-H / C-C C-N C-O C = O C-Si Example 1 63.5 14.5 15.5 6.0 0.5 Example 2 65.0 12.5 16.0 5.0 1.5 Example 3 66.5 10.5 17.0 3.0 3.0 Example 4 69.0 8.0 18.0 0 5.0 Example 5 70.0 6.0 18.5 0 5.5 Comparative Example 1 62.5 16.0 15.0 6.5 -

Referring to Table 2, no CO peaks were seen in Examples 4 and 5, meaning that the polar carbonyl group was covered by the bulk group of the sample. On the other hand, the C-Si peak appears very strong in Examples 4 and 5, suggesting that the concentration of silicon on the surface is very high in both cases.

Mechanical properties

Table 3 shows the results of final tensile strength, Young's modulus and elongation at break in all examples.

Particle size
(nm) Molecular Weight
(Mn) Modulus
(MPa) The tensile strength
(MPa) Elongation at Break
(%) Example 1 (WBPSUU1) 76 23000 4.9 31 692 Example 2 (WBPSUU2) 91 21000 4.7 29 681 Example 3 (WBPSUU3) 105 20000 4.0 22 653 Example 4 (WBPSUU4) 115 16000 2.0 15 350 Example 5 (WBPSUU5) 126 12000 1.0 6 156 Comparative Example 1 (WBPU) 70 25000 5.0 32 698

Referring to Table 3, the aqueous polyurethane of Comparative Example 1 showed the maximum tensile strength and modulus. In comparison, the aqueous polysiloxane urethane ureas of Examples 1 to 5 exhibited relatively low tensile strength, modulus and elongation at break compared to Comparative Example 1. In particular, all of the mechanical properties in the examples can be seen to decrease with increasing content of PDMS. In the case of Example 3, the two polyols exhibited very different polarities and the mechanical properties were degraded by promoting phase separation which could degrade the mechanical properties of the polymer. On the other hand, in the case of Example 5, the phase separation reached a critical point, so that a very weak interfacial adhesion occurred, and the characteristics rapidly decreased. Therefore, it can be seen that in order to obtain excellent mechanical properties in the polysiloxane urethane urea according to the present invention, appropriate control between phase separation and interfacial adhesion is required.

AFM  analysis

6 shows AFM 3D topography of aqueous polyurethanes (a) and aqueous polysiloxane-urethane-ureas ((b)-(c)) according to one embodiment of the invention. Referring to FIG. 6, it can be seen that (b) of Example 4 shows the smoothest state, and the more abundant the silicon moieties exist on the coating surface, the smoother and smoother the surface becomes. It is consistent with XPS analysis result.

Antifouling properties

Antifouling properties were evaluated through visual observation of the coated panels immersed in the resins according to Examples 1 to 5 and Comparative Example 1. Corrosion and adhesion properties were also evaluated through visual inspection. 7 is 1 month (a), 2 months (b), 3 months (c) after immersing the aqueous polyurethane and aqueous polysiloxane-urethane-urea according to Examples 1 to 5, Comparative Example 1 of the present invention in seawater The photograph of the sample surface is then shown. In addition, the results of the experiment are shown in Table 4.

Immersion period (days)
Pollution Area (%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 30 77 76 73 2 2 78 60 88 85 81 3 4 96 90 97 91 88 5 6 99

Referring to Table 4, the degree of corrosion in Examples 1 to 5 was shown to decrease according to the amount of PDMS used, slightly decreased in Examples 2 and 3, and greatly reduced in Examples 4 and 5. Indicated. In the case of Comparative Example 1, various forms of corrosion, such as a scallop, an oyster, and a thin slime of an algae mat, were generated. Contaminated areas accounted for 99% of the total.

From the results of the above example, it can be seen that when the content of PDMS falls within a specific numerical range, since the coating surface is very smooth and slippery, it acts as an antifouling agent, thereby significantly reducing contamination or corrosion.

It can be seen that the aqueous polysiloxane-urethane-urea polymer according to the present invention has antifouling performance by itself, and generally uses PDMS together with pigments and other additives without separately including antifouling agents used in antifouling paints. By controlling appropriately, it can be used as antifouling paint. Therefore, the aqueous polymer dispersion according to the present invention can be said to be very environmentally friendly because it can cope with marine pollution caused by the antifouling agent.

Claims (6)

A resin composition for an antifouling paint comprising an aqueous polysiloxane-urethane-urea dispersion represented by the following Chemical Formula 1, wherein the water occupies in the dispersion is 20 to 80% by weight of the total dispersion.
[Formula 1]

In this formula,
Ut is a urethane group, Ur is a urea group,
R ₁ and R ₂ are linear alkyl groups having 1 to 3 carbon atoms,
n is an integer from 1 to 50.
delete The method of claim 1,
The number average molecular weight (Mn) of the polysiloxane-urethane-urea is 5,000 to 35,000, the resin composition for antifouling paint.
The method of claim 1,
The polyol for preparing the aqueous polysiloxane-urethane-urea is a hydroxy-terminated polydimethylsiloxane (PDMS) and polytetramethylene oxide glycol (PTMG).
5. The method of claim 4,
The hydroxy-terminated polydimethylsiloxane (PDMS) content in the dispersion is 15.0 to 25.0% by weight resin composition for antifouling paint, characterized in that.
The antifouling coating film formed from the resin composition for antifouling paints in any one of Claims 1-5.

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