KR101158935B1 - Sealer coat composition for non-toxic antifouling coating - Google Patents

Abstract

The present invention relates to a non-toxic silicone antifouling paint intermediate composition, and more particularly, by including a binder, an adhesion promoting resin, a curing agent, a curing accelerator, a coating film reinforcing material, an adhesion promoter, thereby maximizing adhesion promotion and strength reinforcing effects. One non-toxic silicone antifouling paint relates to an intermediate composition.

Description

Medium composition for non-toxic silicone antifouling paints {SEALER COAT COMPOSITION FOR NON-TOXIC ANTIFOULING COATING}

The present invention relates to a non-toxic silicone antifouling paint intermediate composition for use in a silicone rubber antifouling paint system for preventing marine organisms from being contaminated by marine structural inlets, nuclear intake pipes, and outer shells of ship bottoms. The present invention relates to a non-toxic silicone antifouling coating composition for maximizing adhesion promotion and strength reinforcing effects by comprising an adhesion promoting resin, a curing agent, a curing accelerator, a coating reinforcing material, and an adhesion promoting agent.

Since the use of organic tin-based antifouling paints containing organic tin has been banned in full since the agreement of the International Maritime Organization since 2003, tin free antifouling paints are the most widely used. Tin-free antifouling paints are manufactured by mixing a copper oxide and an organic antifouling agent as a binder with a resin that does not contain tin and has a performance of slowly eluting in seawater. And the toxicity of organic antifouling agents has been raised, and has a problem that should be repainted every 1 to 5 years.

A technique for preventing the adhesion of marine organisms by minimizing the surface energy of the coating film with the advanced technology compared with such an eluted product has been proposed. Specifically, in order to lower the surface energy of the surface of the coating film, a room temperature-curable liquid silicone rubber in which a polydimethylsiloxane (PDMS) -type polysiloxane polymer having a curable functional group is cured by using a silane compound as a crosslinking agent, and a silicone oil containing some alkyl or aryl groups, or Techniques for producing antifouling paints using a mixture of lubricant components and the like have been introduced.

In addition, acrylic silicone type and fluorine functional group incorporating silicone functional group into acrylic resin have been proposed, but in order to exhibit antifouling performance, it has to combine minimum surface energy and smooth and smooth coating surface property which marine life cannot attach. Therefore, it can be said that the method using a silicon compound is the most prevalent to the next generation nontoxic antifouling coating technology.

The most difficult point in the field application of non-toxic antifouling paint using liquid silicone rubber is the problem of reinforcing the low mechanical strength of the liquid silicone rubber.

The tensile and fracture strengths of the silicone coating are so weak that the coating is easily damaged by a weak physical impact. In addition, the adhesion and compatibility with the rust preventive under given in the ship coating system is weak and can not guarantee durability.

EP 0032597 describes a method of reinforcing the strength of silicone rubber by grafting a polymer containing unsaturated vinyl groups such as butyl acrylate or styrene in liquid silicone rubber with silicone rubber, US Patent No. 5017322 Describes a method of reinforcing strength by forming a network in which silicone rubber and polyurethane or polyurea are mixed.

However, the above method can be used to reinforce the strength of the silicone rubber coating, but the silicone rubber itself has a significant reduction in the smooth and smooth surface properties, there is a difficulty in reducing the antifouling performance.

The second difficulty in the application of liquid silicone rubber is its low adhesion with other materials. In general, anticorrosive coating for marine coating is rubber, vinyl paint, and epoxy paint. Among them, two-component epoxy paints have been widely applied due to excellent corrosion resistance, abrasion resistance, and ease of subsequent coating. However, in order to develop antifouling performance of silicone antifouling paint, it is necessary to maintain low surface energy, to have large releasability, and also due to the effect of raw materials for antifouling expression such as silicone oil present inside the coating film, and elasticity of the coating film itself. Silicone antifouling paints have very poor adhesion with two-component epoxy antirust coatings and other one-component antirust coatings.

In order to solve this problem, it is common to use a method of introducing a middle coating for promoting adhesion between the silicon-based antifouling paint and the anti-rust coating. Japanese Patent Application Laid-Open Nos. 53-137233, 53-137234, 53-137231, etc., describe a method for enhancing adhesion by using a mixture of polybutyral resin and silicone resin, polyurethane or chloroprene and neoprene rubber. Doing. In particular, Japanese Patent Application Laid-Open No. 53-137234 proposes a method of using a mixture of a polymer and a silicone compound reacted with a polyol and an isocyanate.

However, this method shows the effect of promoting adhesion between the silicone antifouling paint and the anti-rust coating, but its adhesion is not sufficient to maintain the life of the antifouling paint for a long period of time, and its application thickness is about 30 to 40 탆. There is a problem that it does not affect the strength reinforcement of the paint top coat at all.

The present invention exhibits an affinity for two coating films of silicone antifouling paint and antirust coating at the same time, thereby improving the antifouling performance of the silicone antifouling coating and at the same time with the antirust coating which has been a problem through physical / chemical combination with the antirust coating. In addition to maximizing the adhesion performance, it is an object of the present invention to provide a non-toxic silicone antifouling composition for reinforcing the mechanical strength.

The intermediate composition for non-toxic silicone antifouling paints according to the present invention includes 1 to 20 parts by weight of resin for promoting adhesion, 1 to 30 parts by weight of a curing agent, 0.01 to 30 parts by weight of a curing accelerator, and 1 to 20 parts of a coating reinforcement based on 100 parts by weight of a binder. It is made by including 1 part by weight to 20 parts by weight and adhesion promoter, characterized in that to maximize the effect of adhesion enhancement and strength.

In the present invention, it is preferable to use at least one of a silicone and a silicone-modified binder having a structure of Formula 1 below as a binder.

Where m is an integer from 30 to 2,000,

R is a hydrogen group, a hydroxyl group, a linear branched alkyl group, an alkoxy group, an acid group, a cyanine group, an amino group, or an epoxy group. R ₁ may be the same as or different from each other, and is a hydrogen group, a hydroxyl group, a linear branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, an aryl group, or a fluorine-containing organic residue.)

Preferably, the binder has a molecular weight of 1,000 to 150,000. If the molecular weight is less than 1,000, the tensile strength of the coating film and the coating film riseability are poor, and if the binder exceeds 150,000, the workability and the appearance of the coating film are poor. Disadvantages may appear.

In addition, the hardness of the binder is preferably a hardness measuring instrument (shore A type) of 40 ~ 120, which is the minimum hardness that can withstand the impact of friction with sea water and impact impact, such as sea floating when applied to marine structures and ships Means. If the hardness is less than 40, irregularities and surface smoothness caused by scratching of the surface may occur. If the hardness exceeds 120, excessive peeling and wrinkles may occur due to excessive elasticity difference between the silicon top and the top. Therefore, it is not preferable.

Adhesion promotion resin used in the present invention increases the strength of the coating film in the coating film and serves to promote adhesion to the roadway, and is widely used to improve general paint properties such as controlling the viscosity, flowability, and reducing dust during coating. As the component involved, it is preferable to use at least one of compounds having the structure of the following formula (2) such as halogenated polyolefin.

Where r is an integer from 1 to 2000,

R ₃ is a halogen element, R ₄ may be the same or different, and is a hydrogen group, a linear or branched alkyl group having 1 to 2 carbon atoms, or a phenyl group.)

The adhesion promoting resin is preferably used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the binder. When the amount is less than 1 part by weight, it is difficult to obtain a desired degree of adhesion effect, and when the amount is more than 20 parts by weight. There is a difficulty in application in the field by halving the adhesion promoting effect of the adhesion promoting resin, inhibiting the expression of paint and paint properties, and thus reducing the mechanical strength and adhesion performance by the unreacted material remaining during the curing process. Not desirable

The curing agent used in the present invention is a component that determines the strength and adhesion of the coating film when the binder forms the coating film, and it is preferable to use one or more of the compounds having the structure of Formula 3 or Formula 4, which is a silane compound. desirable.

(Where s is an integer from 1 to 4,

R ₅ may be the same as or different from each other, and is a methyl group, an ethyl group, a methoxy group, or an ethoxy group,

R ₆ is an alkyl group containing 1 or 2 primary or secondary amine groups such as amino group, N-aminoalkylamino group, N-phenylaminoalkyl group or aminoalkyl group, glycidoxy group, epoxycycloalkyl group, methacryloxy group, Acryloxy group, vinyl group, ureido group, chloro group, mercapto group, or isocyanate group.)

Where t and u are integers from 1 to 4, t + u = 4,

R ₇ and R ₈ may be the same as or different from each other, and are a hydrogen group, a phenyl group or a linear or branched alkyl group having 1 to 4 carbon atoms,

R ₉ is a linear or branched alkyl group having 1 to 3 carbon atoms, a vinyl group, or a phenyl group.)

Examples of the silicone compound corresponding to the curing agent include alkyloxymino silane, alkylkethymioxy silane, acyloxy silane, dialkyldimethoxy silane, alkyltrimethoxy silane, dialkyldiethoxy silane, alkyltriethoxy silane and tetrae. Although there are oxy silane and the like, these examples do not limit the present invention.

The curing agent is preferably used 1 to 30 parts by weight with respect to 100 parts by weight of the binder, when the amount is less than 1 part by weight it is difficult to achieve the desired performance, when it exceeds 30 parts by weight unreacted material remaining after completion of curing It is not preferable because the strength of the coating film may be lowered and the adhesion performance may be degraded due to the influence of the coating film.

The curing accelerator used in the present invention is a component for controlling the curing rate, it is preferable to use a metal compound, and the corresponding metal compounds include titanium compounds, tin compounds, zirconium compounds, etc., these are used alone or mixed It is possible. Titanium compounds include tetraisopropyl titanate, tetra-n-butyl titanate, titanium acetyl acetonate, and the like, and tin compounds include dibutyltindilaurate, tributyltinoxide, and the like, and these examples limit the present invention. It is not.

Preferably, the curing accelerator is used in an amount of 0.01 to 30 parts by weight based on 100 parts by weight of the binder. However, when the amount is less than 0.01 parts by weight, it is difficult to achieve a desired degree of curing effect. It is not preferable because it may halve the enhancement effect, cause difficulty in the field use due to excessive increase in the curing rate, and reduce the mechanical strength and adhesion performance by the unreacted material left after the reaction is completed.

In use, the curing agent and the curing accelerator may be mixed and stored in a one-pack form with a binder, but when long-term storage of more than one year is required, the two-part form of Part A, Part B, or Part A, Part B, Part C It is stored separately in 3 parts and can be mixed before use.

The coating film reinforcing material used in the present invention, as a component for reinforcing the strength of the coating film and controlling the viscoelasticity, it is preferable to use hydrophobic fine silica or titanium oxide.

The coating film reinforcing material is preferably used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the binder. When the amount is less than 1 part by weight, it is difficult to exert its strength reinforcing performance, and when it exceeds 20 parts by weight, the coating film is more than necessary. Rigidity, rather, lowers the general physical properties of the coating, and in particular negatively affects the adhesion performance.

The adhesion promoter used in the present invention is a component used to enhance adhesion with the undercoat and sealer coating film applied to ships, and among the compounds having the structure represented by the following formula (5) or (6) which is a silane compound including an epoxy group or an amine group It is preferable to use 1 or more types.

Where p is an integer from 1 to 4,

R ₁₀ may be the same or different and is a methoxy group, an ethoxy group or a linear or branched alkyl group having 1 to 3 carbon atoms.)

Where w and x are integers from 1 to 4,

R ₁₁ may be the same as or different from each other, a hydrogen group, a linear or branched alkyl group having 1 to 3 carbon atoms, and R ₁₂ is a hydrogen group, a hydroxyl group, a methoxy group, an ethoxy group, a linear or branched alkyl group having 1 to 3 carbon atoms .)

Preferably, the adhesion promoter is a reactive silane, and the reactive silane participates in the curing reaction with the binder according to the reactive functional group and reacts with the unreacted functional group in the undercoat to express the adhesion performance enhancing effect. It does not limit the invention.

The adhesion promoter is preferably used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the binder. When the amount is less than 1 part by weight, it is difficult to express its performance, and when it exceeds 20 parts by weight, curing of the coating film is considerably unstable. Not only can adversely affect the hardness of the coating film, but can also inhibit adhesion with the top coat.

In addition to the above essential ingredients, the intermediate composition of the present invention may further include conventional additives such as pigments as necessary.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Example]

In the following examples and comparative examples, component A (binder), component B (resin for adhesion promotion), component C (curing agent), component D (hardening accelerator), component E (film reinforcing material), component F (adhesion enhancer) are essential The intermediate coating product was manufactured by combining as shown in Table 1 as a component, and the unit in the following Example and a comparative example is a weight part.

Antifouling paint  ingredient

Component A

A-1: Dimethyl silane whose terminal is alkoxy and number average molecular weight is 20,000

A-2: Dimethyl silane having hydroxyl at the terminal and number average molecular weight of 20,000

Component B

B-1: halogenated polyolefin

Component C

C-1: Methyltrimethoxy silane

C-2: tetraethyl orthosilicate

C-3: methyl trismethyl ethyl oxymino silane

Component D

D-1: Dibutyl Tin Dilaurate

D-2: tetra isopropyl titanate

Component E

Hydrophobic Amorphous Fine Silica (Aerosil)

Component F

F-1: KBE-403 (Shin-Etsu)

F-2: KBE-903 (Shin-Etsu)

F-3: KBM-603 (Shin-Etsu)

Part  Manufacture of A

Xylene was added first and then components A and C were added to the contents of Table 1 in a nitrogen blowing state, followed by stirring for about 10 minutes to disperse. Components D were added to the contents of Table 1 and stirred for another 5 minutes. Part A was prepared.

Part  Manufacture of B

Components B, E, and F were added in the amounts shown in Table 1 below, followed by stirring for 5 minutes to prepare Paint Part B.

[Table 1]

Antifouling paint intermediate manufacturing ingredient list

Of test specimen  Manufacturing and Adhesion  exam

Part A and B prepared as described above were mixed just before the coating and stirred for about 5 minutes, and then subjected to the adhesion test on the anti-rusting degree as follows.

After steel specimens (150mm × 300mm × 2mm) are blast pretreated in the state of Sa2 semi-na-metal, three kinds of rust resistant rubber, vinyl, and epoxy type anti-corrosive coatings are coated with airless spray with a dry coating thickness of 250㎛ for 24 hours. It was dried to prepare a coating specimen under antirust.

Twelve kinds of silicone coating materials of Preparation and Comparative Examples prepared on the prepared rust-prevented specimens were coated with an airless spray so as to have a dry coating thickness of 100 μm, followed by drying for 24 hours, and then adhesion test.

The adhesion test is knife scratching, which measures the frequency at which peeling occurs between the middle silicon and the anti-rusting degree in five places of the specimen. Very good ★ (no peeling), excellent ◎ (one peeling), normal ○ (two peeling), poor (triangle | delta) (3-4 peeling), and bad X (5 or more peeling). The adhesion test results are shown in Table 2 below.

[Table 2]

Adhesion test results of silicon intermediate and various rust preventive

As can be seen from the above test results, when the component B is not present in the comparison of Examples 1, 2, 3 and Comparative Examples 2, 3, 4, the adhesion performance between the silicon intermediate and the rust preventive degree is It can be seen that it is ten compared with the case where it exists, and it can be seen that component B is an essential element in securing stable adhesion performance.

In the case of Comparative Example 1, due to the excess silica, the silicon intermediate coating film showed more than necessary hardness, wrinkles occurred during the subsequent coating showed a state that can not be measured, which means that there is a lack of adhesion to the rust preventive.

It can be seen that C3 in the blended components is very positive in terms of adhesion expression compared to C1 or C2.

Impact  exam

After applying the airless spray to the specimen prepared by the same method as the adhesion test specimen, the top coat of the silicone type antifouling paint to a dry coating thickness of 200㎛, the impact test (100cm height, 250g weight) was carried out, Comparative tests were performed with the other types of intermediate coatings. The results are shown in Table 3 below.

Very good ★ (No peeling), Excellent ◎ (1 peeling), Normal ○ (2 peeling), Poor △ (3 ~ 4 peeling) ) And the defect X (5 or more peelings) are divided and described.

[Table 3]

Impact test results after top coat of silicone antifouling paint

As shown in Table 3, it was confirmed that when the silicon medium is used, there is an effect of preventing damage to the coating film due to the increase in elasticity, and the difference in impact test results may occur due to the difference in elasticity and adhesion performance depending on the composition. Confirmed that it can.

The intermediate composition for non-toxic silicone antifouling paint prepared by the present invention can improve the antifouling performance of the silicone antifouling paint, and can not only enhance adhesion to the antirust coating, but also reinforce mechanical strength to resist physical damage. It can have resistance, there is an advantage that can maximize the adhesion promotion and strength reinforcement effect.

Claims (5)

1 to 20 parts by weight of the resin for promoting adhesion, which is one or more of the compounds having the structure of Formula 2, based on 100 parts by weight of the binder having one or more types of silicone and a silicone-modified binder having the structure of Formula 1, Or 1-30 parts by weight of a curing agent of at least one compound having a structure of Formula 4, 0.01-30 parts by weight of a curing accelerator selected from the group consisting of titanium compounds, tin compounds and zirconium compounds, hydrophobic finely divided silica or titanium oxide Intermediate composition for non-toxic silicone antifouling paint comprising 1 to 20 parts by weight of a phosphor coating film reinforcement, and 1 to 20 parts by weight of an adhesion promoter for at least one compound having a structure of Formula 5 or 6 below: [Formula 1]

Where m is an integer from 30 to 2,000, R is a hydrogen group, a hydroxyl group, a linear branched alkyl group, an alkoxy group, an acid group, a cyanine group, an amino group, or an epoxy group, and R ₁ may be the same or different from each other, and a hydrogen group, a hydroxyl group, or a linear branched alkyl group having 1 to 4 carbon atoms. , Alkoxy group, aryl group, or fluorine-containing organic residue.) [Formula 2]

Where r is an integer from 1 to 2000, R ₃ is a halogen element, R ₄ may be the same or different, and is a hydrogen group, a linear or branched alkyl group having 1 to 2 carbon atoms, or a phenyl group.) (3)

(Where s is an integer from 1 to 4, R ₅ may be the same as or different from each other, and is a methyl group, an ethyl group, a methoxy group, or an ethoxy group, R ₆ is an alkyl group containing one or two amino groups, a primary or secondary amine group, or an aminoalkyl group, a glycidoxy group, an epoxycycloalkyl group, a metaacryloxy group, an acryloxy group, a vinyl group, a ureido group, a chloro group , Mercapto group, or isocyanate group.) [Formula 4]

Where t and u are integers from 1 to 4, t + u = 4, R ₇ and R ₈ may be the same as or different from each other, and are a hydrogen group, a phenyl group or a linear or branched alkyl group having 1 to 4 carbon atoms, R ₉ is a linear or branched alkyl group having 1 to 3 carbon atoms, a vinyl group, or a phenyl group.) [Chemical Formula 5]

Where p is an integer from 1 to 4, R ₁₀ may be the same or different and is a methoxy group, an ethoxy group or a linear or branched alkyl group having 1 to 3 carbon atoms.) [Formula 6]

Where w and x are integers from 1 to 4, R ₁₁ may be the same as or different from each other, and is a hydrogen group, a linear or branched alkyl group having 1 to 3 carbon atoms, and R ₁₂ is a hydrogen group, a hydroxyl group, a methoxy group, an ethoxy group, a linear or branched alkyl group having 1 to 3 carbon atoms. .) The intermediate composition for non-toxic silicone antifouling coating according to claim 1, wherein the binder has a number average molecular weight of 1,000 to 150,000 and a hardness of 40 to 120. delete delete delete