JP2007162031A - Antifouling coating composition, coating film formed from antifouling coating composition, antifouling method using antifouling coating composition and hull or underwater structure coated with coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifouling coating material composition capable of forming a coating film having an excellent crack resistance and release resistance under dried conditions. <P>SOLUTION: The antifouling coating material composition includes a coating film-forming copolymer having 20 to 65% by weight component unit derived from a trialkylsilyl ester of polymerizable unsaturated carboxylic acid and having 1,000 to 50,000 number-average molecular weight and zinc oxide in an amount of 1 to 1,000 parts by weight based on 100 parts by weight of coating film-forming copolymer. The coating film is formed of the antifouling coating material composition. The antifouling method comprises using the antifouling coating material composition. The ship body or underwater structure is coated with the coating film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an antifouling coating composition, a coating film formed from the antifouling coating composition, an antifouling method using the antifouling coating composition, and a hull or an underwater structure coated with the coating film. .
More specifically, the present invention is excellent in the strength of the coating film, for example, can form a coating film having a strength capable of suppressing damage to the coating on the wood part where a large pressure is applied particularly during ship construction. Excellent resistance to cracking and peeling in alternating environments (dry and wet alternating parts), for example, immersion in seawater and exposure to air, such as in the vicinity of the waterline of a ship or the waterline of an underwater structure It is possible to form a coating film that is resistant to changes over time even in an environment where it is repeated and has excellent stability, and also has a stable scouring ability in seawater, such as ship bottoms, underwater structures, fishing nets, etc. Self-abrasive antifouling paint composition capable of effectively preventing adhesion of aquatic organisms to the surface, a coating film formed from the antifouling paint composition, an antifouling method using the antifouling paint composition, and Hull covered with the coating The other is related to underwater structures.

  The bottom of the ship, underwater structures, fishing nets, etc. are exposed to water for a long period of time, and animals such as shellfish and barnacles, algae such as laver (seaweed), or various aquatic organisms such as bacteria adhere to the surface. Breeding can impair the appearance and impair its function.

  In particular, when such aquatic organisms adhere to and propagate on the bottom of the ship, the surface roughness of the entire ship increases, and there is a high risk of causing a decrease in ship speed and an increase in fuel consumption. Moreover, to remove such aquatic organisms from the ship bottom, a great amount of labor and work time are required at the dock. In addition, when bacteria adhere to and propagate on underwater structures or the like and slime (sludge-like material) adheres, they may rot, causing damage such as deterioration of physical properties and a significant decrease in life.

  For this reason, conventionally, research and development of various antifouling paints has been made only from the viewpoint of preventing the above-described damage in a portion such as a ship bottom that is immersed in water exclusively. In other words, in the past, it was practically used in consideration of the point that it was applied to parts where alternating dry and wet conditions were repeated, such as the waterline part of the hull and the vicinity of the waterline of the underwater structure, and the coating film strength in the board part. Research and development have not been conducted from the viewpoint of designing extremely useful antifouling paints.

  For this reason, the present inventors are particularly excellent in crack resistance and peel resistance in dry and wet alternating portions, and are repeatedly immersed in seawater and exposed to air, for example, in the waterline portion of a ship. In such environments, it is possible to form a coating film that does not easily change over time and has excellent stability, and has particularly practical strength, such as a place where large pressure is applied, such as a wood block during ship construction. In an effort to find a self-polishing antifouling paint composition that can form a coating film that can suppress damage even in the case of, a surprisingly two component of a specific silyl ester copolymer and zinc oxide The antifouling paint composition containing a specific amount of is excellent in crack resistance and peeling resistance particularly in alternating wet and dry parts, and is stable and resistant to changes over time even in alternating dry and humid environments such as waterline parts of ships. Excellent in sex In addition to these components, in addition to these components, chlorinated paraffins and antifouling agents are also found. In the antifouling paint composition containing the above, it has been found that adhesion of aquatic organisms to the ship bottom, underwater structures, fishing nets and the like can be effectively prevented, and the present invention has been completed.

Conventionally, various antifouling paints have been applied to the bottom of the ship in order to prevent aquatic organisms and the like from being attached to parts such as the bottom of the ship that are immersed in water. As such an antifouling paint,
Examples thereof include those containing a copolymer of tributyltin methacrylate and methyl methacrylate and cuprous oxide (Cu ₂ O). The copolymer in the antifouling coating is hydrolyzed in seawater to give bistributyltin oxide (tributyltin ether, Bu ₃ Sn—O—
Releases organotin compounds such as SnBu ₃ : Bu is a butyl group) or tributyltin halide (Bu ₃ SnX: X is a halogen atom) and exhibits an antifouling effect, and the hydrolyzed copolymer itself is also water-soluble. Since it is a “hydrolyzable self-polishing paint” that dissolves and dissolves in seawater, the resin paint residue does not remain on the ship bottom coating surface, and an active surface can always be maintained.

  However, such organotin compounds are highly toxic and may cause marine pollution, generation of malformed fish, adverse effects on the ecosystem due to the food chain, etc. Development is required.

As such an antifouling paint not containing tin, for example, JP-A-4-264170 (Patent Document 1), JP-A-4-264169 (Patent Document 2), JP-A-4-264168 (Patent Document 1). Examples thereof include silyl ester antifouling paints described in Reference 3). However, in these publications, what is the resistance to cracking of the coating film obtained in particular, or the stability of change over time in an environment in which immersion in water and exposure to dry air are repeated? Not taught.

  These antifouling paints are inferior in antifouling properties as taught in JP-A-6-157951 (Patent Document 4), JP-A-6-157940 (Patent Document 5), etc. There is also a problem that cracks and peeling occur in water.

JP-A-2-196869 (Patent Document 6) discloses a carboxylic acid blocked by a trimethylsilyl group obtained by copolymerizing trimethylsilyl methacrylate, ethyl methacrylate and methoxyethyl acrylate in the presence of an azo polymerization initiator. An antifouling paint containing a blocked acid functional copolymer (A) containing a group and a compound (B) of a polyvalent cation is taught, and the specific description of the invention includes a marine Examples of biocides for organisms include zinc oxide, cuprous oxide, and the like, and examples thereof include chlorinated paraffin plasticizers in addition to the acid functional copolymer (A) and polyvalent cation compounds. An antifouling paint containing is disclosed. However, the coating film obtained from the antifouling paint disclosed in this example has a problem that the crack resistance (particularly, crack resistance during drying) and the peel resistance are not sufficiently satisfactory. That is, in Japanese Patent Laid-Open No. 2-196869,
A coating made of an antifouling paint containing any amount of zinc oxide is particularly excellent in crack resistance and peeling resistance during drying, and in an environment where immersion in seawater and exposure to dry air are repeated. However, nothing is taught about whether it is difficult to change with time and is excellent in stability.

JP-A 63-215780 (Patent Document 7) describes copolymerization of vinyl monomers having an organosilyl group, such as trialkylsilyl esters of (meth) acrylic acid, with other vinyl monomers. Thus, a resin for antifouling paint having a number average molecular weight of 3000 to 40000 is described. In the detailed description section of the invention, an organic water binder such as trimethyl orthoformate and an anti-fouling agent such as cuprous oxide are further described. Although it is described that pigments such as stains and bengara can be blended, the resin composition for antifouling paints described in this publication is particularly inferior in crack resistance at the time of drying and peel resistance, and also in water. In an environment where immersion and exposure to (dry) air are repeated, there is a problem that it is easy to change with time and is less stable.

In addition, Japanese Patent Publication No. 5-32433 (Patent Document 8) corresponding to the above Japanese Patent Publication No. 60-500342 discloses a poisonous substance (a) and a formula [(-CH ₂ -CXCOOR)-(B)-: X H or CH ₃ , R represents SiR ′ ₃ or Si (OR ′) ₃ , R ′ represents an alkyl group, and B represents an ethylenically unsaturated monomer residue]. And an antifouling paint comprising a polymer binder (b) having a specific hydrolysis rate and the like, zinc oxide is exemplified as the antifouling poison (a), a solvent, a water sensitive pigment component, It is described that it can contain an inert pigment, a filler, and a retarder, and in the section of the preparation example of the test paint of JP-A-60-500452, the tributyltin methacrylate polymer (TBTM) and the first oxide An antifouling paint containing copper and the like is described, and silyl acrylate is substituted for this TBTM. The coating film obtained from the antifouling paint actually disclosed in this production example is inferior in crack resistance, particularly crack resistance during drying, and in the vicinity of the water line, etc. However, there is a problem that it is easy to change with time and is inferior in stability.

In JP-A-7-18216 (Patent Document 9), A) In the molecule, the formula: —COO—SiR ¹ R ²
The main component is an organosilicon-containing polymer having a triorganosilicon ester group represented by R ³ (R ^{1 to} R ³ represent an alkyl group having 1 to 18 carbon atoms), and B) copper or a copper compound. In the coating composition to be used, as an essential component other than the components A and B, the formula C):

(R ^{4 to} R ⁶ represent a hydrogen atom, an alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group, etc., R ⁷ represents an alkyl group having 1 to 18 carbon atoms, and n represents an integer of 1 to 3). A coating composition containing an alkoxy group-containing silicon compound represented by the formula (1) is disclosed, and in the column of the constitution and action of the invention of the publication, the coating composition includes a pigment such as zinc oxide, chlorine It describes that a plasticizer such as chlorinated paraffin and a resin such as acrylic resin may be included as necessary. In the examples, a coating composition containing a tri-n-butylsilyl methacrylate polymer, zinc oxide, a petiole, talc and the like is disclosed. However, this publication does not teach anything about the crack resistance of the obtained coating, especially when it is dried, or the stability over time near the water line.
Japanese Patent Laid-Open No. 7-102193 discloses a formula:

(However, in the formula, each of R ^{1 to} R ³ is a group selected from an alkyl group and an aryl group, and may be the same group or different groups. X is an acryloyloxy group. , A methacryloyloxy group, a maleoyloxy group or a fumaroyloxy group) and a formula: Y— (CH ₂ CH ₂ O) _n —R ⁴ (wherein R ⁴ is an alkyl group or an aryl group) And Y is an acryloyloxy group or a methacryloyloxy group, and n is an integer of 1 to 25). A coating composition containing an agent as an essential component is disclosed, and in the section of action and effect of the invention, zinc oxide and the like are exemplified as an antifouling agent, and 0.1 to 80% by weight in the solid content of the coating It is stated that it is used in an amount. However, this publication does not teach anything about crack resistance at the time of drying, particularly the stability of change with time of the obtained coating film.
As described above, in any of the above publications, a coating film composed of an antifouling paint of any composition is repeatedly cracked particularly during drying, or repeatedly immersed in water and exposed to dry air. No teaching is given as to whether it is excellent in stability over time in an environment.
JP-A-4-264170 JP-A-4-264169 JP-A-4-264168 Japanese Patent Laid-Open No. 6-157941 JP-A-6-157940 JP-A-2-196869 JP-A 63-215780 Japanese Patent Publication No. 5-32433 corresponding to the above Japanese Special Publication No. 60-500342 Japanese Patent Laid-Open No. 7-18216

  The present invention seeks to solve the problems associated with the prior art as described above, and is particularly resistant to cracking and peeling, etc. under dry conditions such as being above the waterline of a hull, underwater structure, etc. It is easy to change over time by being exposed to dryness due to fluctuations in the waterline or being immersed in seawater, and can form a coating film with excellent long-term stability. An object of the present invention is to provide an antifouling coating composition capable of forming a coating film having excellent strength capable of suppressing damage caused by pressure even when a pressure such as wood is applied.

  More preferably, the present invention can form an antifouling coating film having excellent crack resistance in water, antifouling properties, and self-polishing properties (consumability) in addition to the above-mentioned purpose, and also has storage stability. An object is to provide an antifouling coating composition that is excellent.

  The present invention also provides a coating film formed from such an antifouling coating composition, an antifouling method using the antifouling coating composition, and a hull or underwater structure coated with the coating film. The purpose is that.

  The antifouling paint composition according to the present invention has a film-forming property having a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight and a number average molecular weight of 3000 to 50000. It is characterized by comprising a copolymer and zinc oxide.

  In the preferred embodiment, zinc oxide is usually contained in an amount of 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, based on 100 parts by weight of the film-forming copolymer. desirable.

  The antifouling paint composition according to the present invention may contain chlorinated paraffin in addition to the above-mentioned film-forming copolymer and zinc oxide. It is desirable that zinc oxide is contained in an amount as described above with respect to 100 parts by weight of the copolymer, and chlorinated paraffin is contained in an amount of 18 to 65 parts by weight, preferably 20 to 55 parts by weight. .

  In a preferred embodiment of the present invention, it is desirable that at least one of the three alkyl groups bonded to the silicon atom of the trialkylsilyl ester has 3 or more carbon atoms. Those having 4 or more carbon atoms in all groups are preferred, and the trialkylsilyl ester is particularly preferably tributylsilyl (meth) acrylate.

The average carbon number of the chlorinated paraffin is 8 to 30, and the chlorine content is preferably 35 to 75%.
The antifouling coating composition according to the present invention has a number average molecular weight compatible with the film-forming copolymer in addition to the film-forming copolymer and zinc oxide (meta ) Acrylic ester-based polymer may be contained, and in such an antifouling coating composition, zinc oxide is contained in an amount of 1 to 1000 parts by weight, preferably 3 parts per 100 parts by weight of the film-forming copolymer. It is contained in an amount of ˜500 parts by weight, and the (meth) acrylic acid ester polymer is contained in an amount of 5 to 200 parts by weight, preferably 10 to 200 parts by weight.

  In such an antifouling coating composition, the compatible (meth) acrylic acid ester polymer is a hydrophobic (meth) acrylic acid ester homopolymer, or two or more (meth) acrylic polymers. Desirably, it is at least one (meth) acrylic acid ester polymer selected from the group consisting of acid ester copolymers and (meth) acrylic acid ester / styrene copolymers. The glass transition temperature (Tg) of the (meth) acrylic acid ester polymer is preferably 0 ° C. or higher.

  The antifouling paint composition according to the present invention may further contain chlorinated paraffin in addition to the above-mentioned film-forming copolymer, zinc oxide, and the above-mentioned (meth) acrylic acid ester-based polymer. Well, in such an antifouling coating composition, zinc oxide is contained in an amount of 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, based on 100 parts by weight of the film-forming copolymer. The acrylate polymer is contained in an amount of 5 to 200 parts by weight, preferably 10 to 200 parts by weight, and the chlorinated paraffin is contained in an amount of 5 to 150 parts by weight, preferably 8 to 100 parts by weight. It is desirable.

  The antifouling paint composition according to the present invention may contain a dehydrating agent in addition to the above-mentioned film-forming copolymer and zinc oxide. Zinc oxide is contained in an amount of 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, based on 100 parts by weight of the polymer, and the dehydrating agent is 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight. It is desirable that it is contained in an amount.

  The antifouling coating composition according to the present invention may contain the above-mentioned film-forming copolymer, zinc oxide, chlorinated paraffin, and a dehydrating agent. Zinc oxide is contained in an amount of 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, and chlorinated paraffin is 3 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the copolymer. It is preferably contained in an amount of 18 to 65 parts by weight, and the dehydrating agent is contained in an amount of 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight.

The antifouling coating composition according to the present invention may contain the film-forming copolymer, zinc oxide, chlorinated paraffin, the (meth) acrylic acid ester polymer, and a dehydrating agent. In the antifouling coating composition, zinc oxide is contained in an amount of 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, and chlorinated paraffin is 3 to 200 parts per 100 parts by weight of the film-forming copolymer. It is contained in an amount of 5 parts by weight, preferably 5 to 150 parts by weight, and the (meth) acrylic acid ester polymer is 1 to 200 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 parts.
The dehydrating agent is contained in an amount of 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight.

  In any of the above antifouling coating compositions according to the present invention, an organic and / or inorganic antifouling agent (excluding zinc oxide) is added in an amount of, for example, 50 to 100 parts by weight based on 100 parts by weight of the film-forming copolymer. It is preferably contained in an amount of about 1500 parts by weight, and among such antifouling agents (biocides), copper or copper compounds (eg, cuprous oxide), zinc pyrithione, and the like are preferable.

Among the antifouling coating compositions according to the present invention, in addition to the film-forming copolymer and zinc oxide, chlorinated paraffin, the (meth) acrylic acid ester polymer, a dehydrating agent or an antifouling agent ( In addition to the above effects, it can form a coating film with excellent resistance to cracking in water, antifouling properties, self-polishing properties (consumability), and storage stability. Is excellent. (In the present specification, unless otherwise specified, the terms “crack resistance and peel resistance” are used to include both in water and in (dry) air.)
The antifouling coating film according to the present invention is formed from the above antifouling coating composition.

  The antifouling method for a hull or underwater structure according to the present invention is characterized by using the antifouling paint composition. The antifouling coating film hull or underwater structure according to the present invention is characterized in that the surface of the hull or underwater structure is coated with a coating film made of the above antifouling coating composition.

According to the one-pack type antifouling paint composition according to the present invention as described above, it is excellent in crack resistance, peel resistance, particularly crack resistance under drying such as being exposed to air, and peel resistance. Forms a coating film with excellent stability over time (that is, it is difficult to change over time even if it is repeatedly exposed to drying due to fluctuations in the waterline, etc., or immersed in water, and has long-term stability). it can.
In particular, in addition to the film-forming copolymer and zinc oxide, the book further contains the chlorinated paraffin, (meth) acrylic acid ester polymer, dehydrating agent, antifouling agent (excluding zinc oxide), etc. In addition to the above effects, the antifouling paint composition of the invention is further excellent in physical properties such as peel resistance to a base material such as a ship bottom or a primer layer, and also excellent in antifouling properties and self-polishing properties (consumability). The antifouling coating film can be formed, and it is excellent in storage stability.

<Anti-fouling paint composition>
Hereinafter, the antifouling paint composition according to the present invention will be specifically described.
The antifouling paint composition according to the present invention contains the following film-forming copolymer and zinc oxide, and the zinc oxide is based on 100 parts by weight of the film-forming copolymer. Usually, it is contained in an amount of 1 to 1000 parts by weight, preferably 3 to 500 parts by weight.

  According to such a one-pack type antifouling paint composition according to the present invention, it is excellent in crack resistance, peel resistance, particularly crack resistance under drying such as exposure to air, and changes with time. Stability (i.e., anti-fouling coatings such as hulls and underwater structures are repeatedly exposed to dryness due to fluctuations in the waterline, etc., and are less likely to change over time, resulting in long-term stability. It is possible to form an excellent coating film.

When the amount of zinc oxide is less than 1 part by weight, for example, when the coating film is exposed to the air such as being exposed to the air, cracks and peeling easily occur, and more than 1000 parts by weight. With regard to the amount, no further improvement in the effect can be expected, and there is a tendency to cause cracks during coating and drying caused by an excessively high pigment concentration, and an increase in the amount of dust during spray coating.
[ Film-forming copolymer ]
The film-forming copolymer has a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight and a number average molecular weight of 3000 to 50000.

  This trialkylsilyl ester is represented, for example, by the following formula [I]:

It is represented by
In this formula [I], R ¹ represents a hydrogen atom or an alkyl group such as a methyl group, and R ² , R ³ and R ⁴ each have 1 carbon atom such as a methyl group, an ethyl group, a propyl group, or a butyl group. It represents about ˜18 alkyl groups, and R ² , R ³ and R ⁴ may be different from each other or the same.

Specific examples of such trialkylsilyl esters include (meth) acrylic acid trimethylsilyl ester, (meth) acrylic acid triethylsilyl ester, (meth) acrylic acid tripropylsilyl ester, and (meth) acrylic acid tributyl. Trialkylsilyl ester having the same R ² , R ³ and R ⁴ , such as silyl ester, (meth) acrylic acid dimethylpropylsilyl ester, (meth) acrylic acid monomethyldipropylsilyl ester, (meth) acrylic acid methylethyl R ² , such as propylsilyl ester
Examples thereof include trialkylsilyl esters in which part or all of R ³ and R ⁴ are different from each other.

In the present invention, such trialkylsilyl esters may be used alone or in combination of two or more.
Among such trialkylsilyl esters, those in which at least one alkyl group of R ² , R ³ and R ⁴ has 3 or more carbon atoms are preferred, and further, the number of carbon atoms of these three alkyl groups preferably it has but at all 4 or more, R ^2, total number of carbon atoms of R ³ and R ⁴ are preferably about 5 to 21.

  Among such trialkylsilyl esters, in particular, the ease of synthesis of trialkylsilyl esters, or the film-forming properties, storage stability, and scouring properties of antifouling coating compositions using such trialkylsilyl esters. In view of the ease of control, (meth) acrylic acid tributylsilyl ester is most preferably used.

As a monomer (comonomer) copolymerized with such a trialkylsilyl ester, any polymerizable unsaturated compound (ethylenically unsaturated monomer) can be used. As such a polymerizable unsaturated compound, Specifically, alkyl (meth) acrylates such as (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid cyclohexyl ester, etc. Examples thereof include styrenes such as esters, styrene and α-methylstyrene, vinyl esters such as vinyl acetate and vinyl propionate, and preferably, methyl methacrylate (MMA) is used.

  Such MMA is usually contained in a comonomer (ethylenically unsaturated monomer) in an amount of usually 30% by weight or more, preferably 50% by weight or more. In the copolymer containing the glass, the glass transition temperature (Tg) is as high as 30 to 60 ° C., for example, and the strength of the coating film made of an antifouling coating composition containing chlorinated paraffin as described later is high. Not lowered.

  The component unit derived from the polymerizable unsaturated compound such as this (meth) acrylic acid alkyl ester and the component unit derived from the trialkylsilyl ester are each used as a raw material in the copolymer. The ethylene bond of the monomer is cleaved and usually bonded randomly.

  In addition, if a carboxylic acid residue is present in such a copolymer, the storage stability of the resulting antifouling coating composition is significantly reduced. It is desirable that is not present.

In the synthesis of the copolymer, it is preferable to use a high-purity monomer having no carboxylic acid residue.
In such a film-forming copolymer, as described above, one or more component units derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid as described above (trialkylsilyl ester) Such a trialkylsilyl ester component unit may be contained in an amount of 20 to 65% by weight, preferably 30 to 55% by weight. It is preferable that it is contained in the antifouling coating composition because an antifouling coating film having excellent long-term antifouling properties can be obtained from this antifouling coating composition.

  Moreover, the number average molecular weight (Mn) of this copolymer by GPC measurement is 3000-50000, Preferably it is 3000-20000, More preferably, it is 4000-15000, Most preferably, it is 5000-12000, Moreover, weight average molecular weight (Mw) ) Is usually 4000-150,000 (150,000), preferably 4000-60000 (60,000), more preferably 6000-30000 (30,000), and the molecular weight distribution (Mw / Mn) of this copolymer ) Is usually 1.0 to 4.0, preferably 1.0 to 3.0, particularly preferably 1.0 to 2.5, and the glass transition temperature (Tg ° C.) of the copolymer. ) Is usually 15 to 80 ° C, preferably 25 to 80 ° C, more preferably 30 to 70 ° C, and particularly preferably 35 to 60 ° C. Preferred, The viscosity of for example, 50% xylene solution of the copolymer (25 ° C., CPS) is usually 30 to 1000, it is desirable that preferably is 40 to 600.

  When the number average molecular weight of this copolymer is within the above range (1000 to 50000), the coating film antifouling performance for a long period of time, the damage resistance (impact resistance) of the formed coating film, and the resulting coating composition The storage stability of the film and the crack resistance of the coating film become excellent.

  Specific examples of such film-forming copolymers include the following, preferably film-forming properties indicated by numbering (1) and (2), more preferably numbering (1). A copolymer is used.

(1): a copolymer of tributylsilyl methacrylate (I) and methyl methacrylate (MMA), the copolymerization ratio ((I) / (MMA): weight ratio) of 35 to 65/65 to 35 (Total component total 100 parts by weight), number average molecular weight (Mn) is 3000 to 50,000, preferably 5000 to 12000, and weight average molecular weight (Mw) is 4000 to 150,000, preferably 6000 to 30000 (3 And a molecular weight distribution (Mw / Mn) of 1.0 to 4.0, preferably 1.0 to 2.5, and a glass transition temperature (Tg ° C) of 30 to 70 ° C, preferably 35. Having a viscosity (25 ° C., CPS) in a 50% xylene solution of 30 to 1000, preferably 40 to 600, for example,

(2): Tripropylsilyl methacrylate (b), methyl methacrylate (MMA) and 2-
Copolymer with ethyl hexyl acrylate (C) and its copolymerization ratio ((b) / (MMA)
/ (C): weight ratio) is 25 to 55/74 to 35/1 to 10 (total 100 parts by weight of all components), and the number average molecular weight (Mn) is 3000 to 50,000, preferably 5000 to 12000. The weight average molecular weight (Mw) is 4000-150,000, preferably 6000-30000 (30,000), and the molecular weight distribution (Mw / Mn) is 1.0-4.0, preferably 1.0-2. 5 and a glass transition temperature (Tg ° C.) of 30 to 70 ° C., preferably 35 to 60 ° C., for example, its viscosity (25 ° C., CPS) in a 50% xylene solution is 30 to 1500, preferably 40 to 1000 things,

(3): A copolymer of tributylsilyl methacrylate (b), tripropylsilyl methacrylate (b) and methyl methacrylate (MMA), the copolymerization ratio ((b) / (b) / (MMA ): Weight ratio) is 30-60 / 1-20 / 69-20 (total 100 parts by weight of all components), number average molecular weight (Mn) is 3000-50,000, preferably 5000-12000, weight average. The molecular weight (Mw) is 4000-150,000, preferably 6000-30000 (30,000), and the molecular weight distribution (Mw / Mn) is 1.0-4.0, preferably 1.0-2.5. The glass transition temperature (Tg ° C) is 30 to 60 ° C, preferably 35 to 55 ° C. For example, the viscosity (25 ° C, CPS) in a 50% xylene solution is 30 to 1000, preferably 40 to 400 ,

(4): A copolymer of tributylsilyl methacrylate (b), tripropylsilyl methacrylate (b), methyl methacrylate (MMA), and 2-ethylhexyl acrylate (c), the copolymerization ratio (( B) / (b) / (MMA) / (c): weight ratio) is 30-60 / 1
To 20/68 to 19/1 to 10 (total component total 100 parts by weight), number average molecular weight (Mn) is 3000 to 50,000, preferably 5000 to 12000, and weight average molecular weight (Mw) is 4000 to 2000. 150,000, preferably 6000-30000 (30,000), molecular weight distribution (Mw / Mn) is 1.0-4.0, preferably 1.0-2.5, and glass transition temperature (Tg ° C. ) Is 30 to 60 ° C., preferably 35 to 55 ° C., for example, having a viscosity (25 ° C., CPS) in a 50% xylene solution of 30 to 1000, preferably 40 to 400,

(5): A copolymer of tributylsilyl methacrylate (I), methyl methacrylate (MMA), and 2-ethylhexyl acrylate (C), and the copolymerization ratio ((I) / (MMA) / (C ): Weight ratio) is 35 to 65 / 64.9 to 34.9 / 0.1 to 10 (total 100 parts by weight of all components), and the number average molecular weight (Mn) is 3000 to 50,000, preferably 5000 to 12000, the weight average molecular weight (Mw) is 4000-150,000, preferably 6000-30000 (30,000), and the molecular weight distribution (Mw / Mn) is 1.0-4.0, preferably 1.0. To 2.5, glass transition temperature (Tg ° C.) of 30 to 70 ° C., preferably 35 to 60 ° C., for example, its viscosity (25 ° C., CPS) in a 50% xylene solution is 30 to 1000, preferably Is from 40 to 600 ,

(6): Copolymer of triisopropylsilyl acrylate (d), methyl methacrylate (MMA) and ethyl acrylate (e), and the copolymerization ratio ((d) / (MMA) / (e): weight) Ratio) is 40 to 65/59 to 20/1 to 20 (total 100 parts by weight of all components), the number average molecular weight (Mn) is 1000 to 50,000, preferably 3000 to 30000 (30,000), and the weight The average molecular weight (Mw) is 1000-150,000, preferably 3000-30,000, the molecular weight distribution (Mw / Mn) is 1.0-4.0, preferably 1.0-3.0, and the glass transition The temperature (Tg ° C.) is 20 to 80 ° C., preferably 25 to 75 ° C., for example, the viscosity (25 ° C., CPS) in a 50% xylene solution is 30 to 1500, preferably 40 to 1300,

(7): A copolymer of triisobutylsilyl methacrylate (f), methyl methacrylate (MMA), and 2-ethylhexyl acrylate (c), with a copolymerization ratio ((f) / (MMA) / (c) ): Weight ratio) is 35 to 65 / 64.9 to 34.9 / 0.1 to 10 (total 100 parts by weight of all components), and the number average molecular weight (Mn) is 1000 to 50,000, preferably 3000 to 12000, the weight average molecular weight (Mw) is 1000-150,000, preferably 3000-30000 (30,000), and the molecular weight distribution (Mw / Mn) is 1.0-4.0, preferably 1.0- 2.5, a glass transition temperature (Tg ° C.) of 25 to 80 ° C., preferably 30 to 70 ° C., for example, its viscosity (25 ° C., CPS) in a 50% xylene solution is 30 to 2000, preferably 40-1500 Of, etc.

In order to prepare such a film-forming copolymer, for example, in an inert solvent such as a nitrogen stream, in an organic solvent such as xylene, a trialkylsilyl ester such as tributylsilyl methacrylate and a comonomer A polymerizable unsaturated compound containing methyl methacrylate in an amount of 50% by weight or more (eg, 80% by weight), an azo type or a peroxide type such as 2,2′-azobisisobutyronitrile, etc. In the presence of a polymerization initiator such as n-octyl mercaptan as necessary, and a reaction such as radical polymerization at a temperature of about 50 to 120 ° C. for about 2 to 12 hours. .

  The film-forming copolymer thus obtained contains each component unit in an amount corresponding to the amount of each monomer used. The polymerization method is not limited to the simple radical solution polymerization method, and various conventionally known methods can be employed.

  The solvent can be arbitrarily selected from various solvents commonly used for paints, such as aliphatics, ketones, esters and ethers, in addition to the aromatics (eg, xylene). As the solvent, a solvent having a low water content is particularly preferable. Use of such a low water solvent is preferable because the hydrolysis reaction during and after the reaction can be avoided.

In addition, since the alcohol solvent has a high initial moisture content and has reactivity with silanol, it is not appropriate to use the alcohol solvent during the reaction from this viewpoint.
[ Production of antifouling paint composition ]
Such an antifouling coating composition can be produced by appropriately using a conventionally known method. For example, the antifouling coating composition can be produced, for example, with respect to 100 parts by weight of the film-forming copolymer and the film-forming copolymer. Zinc oxide in an amount of 1 to 1000 parts by weight, chlorinated paraffin in an amount of 18 to 65 parts by weight as described later, and an antifouling agent in an amount of 50 to 1500 parts by weight (for example, suboxidation) Copper (80-1200 parts by weight), 0.1-200 parts by weight of dehydrating agent (eg, anhydrous gypsum, molecular sieve) and any amount of anti-sagging / precipitating agent, pigment, solvent, etc. Alternatively, they may be added in any order and stirred, mixed, and dispersed.

Such an antifouling coating composition according to the present invention contains a film-forming copolymer and zinc oxide (zinc white). In addition to this, a chlorinated paraffin, an antifouling agent, as described later. It may contain (meth) acrylic acid ester polymer, dehydrating agent, sagging / precipitating agent, scaly pigment, solvent and the like.
[ Chlorinated paraffin ]
That is, in a preferred embodiment of the present invention, the antifouling coating composition may further contain chlorinated paraffin (chlorinated paraffin; salt para) in addition to the film-forming copolymer and zinc oxide. Good.

  In such an antifouling coating composition, zinc oxide is usually contained in an amount of 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, based on 100 parts by weight of the film-forming copolymer. The paraffin is desirably contained in an amount of 18 to 65 parts by weight, preferably 20 to 55 parts by weight.

  Further, in such an antifouling coating composition, the antifouling agent as described later is usually 50 to 1500 parts by weight, preferably 80 to 1200 parts by weight with respect to 100 parts by weight of the film-forming copolymer. It is desirable that it is contained in an amount.

  Chlorinated paraffin is immersed in water (including fresh water and seawater; the same shall apply hereinafter) crack resistance of a coating film (also referred to as “antifouling coating film” in the present specification) comprising the resulting antifouling coating composition. The chlorinated paraffin may be linear or branched and may be liquid or solid (powder) at room temperature. However, those having an average carbon number of usually 8 to 30, preferably 10 to 26 are preferably used, and the number average molecular weight is usually 200 to 1200, preferably 300 to 1100, and the viscosity is usually 1 or more ( (Poise / 25 ° C.), preferably 1.2 or more (poise / 25 ° C.), with a specific gravity of 1.05-1.80 / 25 ° C., preferably 1.10-1.70 / 25 ° C. Preferably used.

When such a carbon number chlorinated paraffin is used, a coating film with little cracking and peeling can be formed using the resulting antifouling coating composition.
In addition, it is preferable that the carbon number of a chlorinated paraffin exists in the range of 8-30 from the suppression effect of a crack, and the consumable property (upgradability) and antifouling property of the coating film surface obtained.

The chlorination rate (chlorine content: wt%) of the chlorinated paraffin is usually 35 to 75%, preferably 35 to 65%.
When chlorinated paraffin having such a chlorination rate is used, a coating film with little cracking and peeling can be formed using the resulting antifouling coating composition.

When the chlorination rate of the chlorinated paraffin is in the range of 35 to 75%, the miscibility (compatibility) with the film-forming copolymer (silyl ester copolymer) and the crack suppressing effect were obtained. Excellent wear and antifouling properties of the coating surface. Examples of such chlorinated paraffin include “Toyoparax 150” and “Toyoparax A-70” manufactured by Tosoh Corporation.

In the present invention, two or more kinds of chlorinated paraffins having different chlorine contents and carbon numbers can be used in appropriate combination.
When two or more kinds of chlorinated paraffins are used in combination, the carbon number and chlorination rate of the chlorinated paraffin are the carbon number or chlorine of these chlorinated paraffins contained in the antifouling coating composition. The average value of the conversion rate is shown.

In the antifouling coating composition according to the present invention, such chlorinated paraffin is used in an amount of 3 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the film-forming copolymer. It is preferably contained in an amount of 18 to 65 parts by weight, more preferably 20 to 55 parts by weight, particularly preferably 20 to 50 parts by weight.

  When the amount of the chlorinated paraffin is in the range of 18 to 65 parts by weight, the effect of suppressing cracks generated in the coating film formed with the antifouling coating composition is excellent, and the coating film strength and damage resistance (impact) resistance. To become better.

  Thus, the antifouling coating composition in which chlorinated paraffin or the like is blended as described above in addition to the above-mentioned film-forming copolymer and zinc oxide is one-component and excellent in storage stability. Even if the coating film (antifouling coating film) made of this antifouling coating composition formed on the ship bottom is exposed to the air and submerged, cracks in the antifouling coating film are suppressed.

Moreover, when this antifouling coating composition is applied to the primer surface, peeling of the antifouling coating film from the applied primer surface is suppressed.
In addition, the antifouling coating film of the present invention has already been applied by coating the bottom of the ship with various antifouling paints, including painting with the antifouling paint composition of the present invention, or by using the antifouling paint composition of the present invention. In the case where repair coating or the like is performed on the surface of the ship bottom or the like formed, peeling of the surface antifouling coating film of the present invention from the surface of the antifouling coating film previously applied and formed is suppressed.

In addition, the antifouling coating film of the present invention applied and formed on the primer surface or the surface of the ship bottom to be repaired in this way can be controlled for consumption, and the necessary degree of wear and prevention can be reduced depending on the environment used. Dirty power (sex) can be provided. Therefore, this antifouling coating composition is economically superior because the film thickness of the antifouling coating film to be formed can be reduced to the maximum according to the application.
[Anti-fouling agent]
The antifouling paint composition according to the present invention does not necessarily contain an antifouling agent, but preferably contains an antifouling agent.

Such an antifouling agent may be organic or inorganic (excluding zinc oxide) and is not particularly limited. Specifically, for example, cuprous oxide ( Cu ₂ O)
In addition to copper or copper compounds such as copper powder, cuprous thiocyanide (rhodan copper), etc., metal-pyrithione and its derivatives represented by the following formula [II] [wherein R ^{1 to} R ⁴ are each independently A hydrogen, an alkyl group, an alkoxy group, a halogenated alkyl group, M represents a metal such as Zn, Cu, Na, Mg, Ca, Ba, Pb, Fe, Al, etc., and n represents a valence]:

, Tetramethylthiuram disulfide, carbamate toxicants (eg zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate), 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,6-trichlorophenylmaleimide, pyridine triphenylborane and rhodan copper, preferably cuprous oxide Is used.

Antifouling agents other than cuprous oxide are preferably used in combination with cuprous oxide. As the antifouling agent used in combination with cuprous oxide, 2-pyridinethiol-1-oxide zinc salt (zinc pyrithione) is used. preferable.

  Such antifouling agents can be used alone or in combination. Such an antifouling agent may be a type of antifouling agent, a film-forming copolymer or the like used in preparing the antifouling coating composition, or a type of ship or the like on which such an antifouling coating composition is applied and formed (ship However, it is not determined more generally than for ocean-going coastal use, various seawater areas, wooden-steel-aluminum ships, etc.), but the antifouling agent is used with respect to 100 parts by weight of the film-forming copolymer. The total amount is usually 50 to 1500 parts by weight, preferably 80 to 1200 parts by weight.

For example, when the cuprous oxide is used as an antifouling agent, the cuprous oxide is usually contained in an antifouling coating composition in an amount of about 80 to 1200 parts by weight with respect to 100 parts by weight of the film-forming copolymer. It may be contained in.
[(Meth) acrylic acid ester polymer]
In the antifouling coating composition according to the present invention, the number average molecular weight compatible with the film-forming copolymer is 1,000 to 100,000 (100,000 (100,000) in addition to the film-forming copolymer and zinc oxide. ) (Meth) acrylic acid ester polymer [a (meth) acrylic acid ester homopolymer or copolymer other than (meth) acrylic acid silyl ester] may be contained.

  In the antifouling coating composition of the present invention, in addition to the film-forming copolymer, zinc oxide and the chlorinated paraffin, a (meth) acrylic acid ester system compatible with the film-forming copolymer. When the polymer is blended, the crack resistance of the resulting coating film can be further improved, the seawater consumption rate of the coating film and the durability of the antifouling performance can be adjusted to a suitable range, and When the antifouling coating composition of the present invention is overcoated on an existing antifouling coating film, there is an advantage that the effect of further improving the adhesion of the obtained coating film can be exhibited. Even if the blending amount of the chlorinated paraffin is reduced, there is an advantage that the crack resistance of the obtained coating film can be improved.

  As the (meth) acrylic acid ester-based polymer compatible with such a film-forming copolymer, (meth) other than the (meth) acrylic acid silyl ester used for preparing the film-forming copolymer. Examples include homopolymers or copolymers of acrylic acid esters, (meth) acrylic acid ester homopolymers, copolymers of at least two (meth) acrylic acid esters, (meth) acrylic acid esters, Examples thereof include styrene copolymers. Such (meth) acrylic acid ester polymers can be used alone or in combination of two or more.

  These (meth) acrylic acid ester-based polymers may be, for example, chain-like or branched as long as they are compatible with the film-forming copolymer, and have a crosslinked structure. Also good.

Here, the film-forming copolymer and the “compatible” (meth) acrylate polymer are a film-forming copolymer (also referred to as a trialkylsilyl (meth) acrylate copolymer) concentration of 30. Weight% xylene solution and (meth) acrylic acid ester polymer concentration 30 weight%
When the xylene solution is mixed at a volume ratio of 1: 1 at 25 ° C., it becomes a transparent homogeneous solution, or a milky white homogeneous solution is formed without forming a two-liquid separation layer (meta ) An acrylic acid ester polymer.

  In addition, if the number average molecular weight of the (meth) acrylic acid ester polymer is in the above range, it is possible to effectively suppress cracking and adjust the degree of wear, and to prevent static contamination. There exists a tendency which can form the antifouling coating film excellent also in the property.

  In addition, when the number average molecular weight of the (meth) acrylic acid ester polymer exceeds the above range, the antifouling coating film obtained has a large effect of suppressing cracks and a large effect of reducing the degree of wear. If the molecular weight of the (meth) acrylic acid ester polymer is smaller than the above range, the antifouling property of the resulting antifouling coating can be kept high, but cracks can be suppressed. The effect tends to decrease.

  Examples of such a (meth) acrylate polymer include, for example, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Homopolymers of (meth) acrylates such as cyclohexyl acrylate and phenyl (meth) acrylate or copolymers of these monomers, aromatic vinyl compounds such as styrene (ST), vinyl acetate, vinyl chloride, ethylene, Examples thereof include copolymers of various monomers such as propylene, butadiene and vinyl ether compounds and (meth) acrylic acid ester monomers.

As such (meth) acrylic acid ester polymer, specifically, for example,
(1): A copolymer of methyl methacrylate (MMA) and butyl methacrylate (BMA), the copolymerization ratio (indicated by the weight ratio of each component, the same shall apply hereinafter) (MMA / BMA) 30-70 / 70-30 (all components total 100 parts by weight), number average molecular weight is 1000-100,000, preferably 1000-50,000,
(2): A copolymer of isobutyl methacrylate (i-BMA), t-butyl methacrylate (t-BMA), styrene (ST) and stearyl methacrylate (SLMA), and the copolymer Ratio (i-BMA
/ T-BMA / ST / SLMA) is 10 to 40/10 to 40/20 to 60/5 to 20 (total of all components 1
00 parts by weight) and a number average molecular weight of 1,000 to 100,000, preferably about 1,000 to 80,000,
(3): A homopolymer of methyl methacrylate (MMA) having a number average molecular weight of 1000
100,000, preferably about 1000 to 20,000,
(4): A homopolymer of ethyl methacrylate (EMA) having a number average molecular weight of 1000
100,000, preferably about 1000 to 20,000,
(5): a copolymer of methyl methacrylate (MMA) and butyl acrylate (BA),
The copolymerization ratio (MMA / BA) is 90 to 10/10 to 90 (total 100 parts by weight of all components), and the number average molecular weight is 1,000 to 100,000, preferably about 1,000 to 50,000,
(6): a copolymer of ethyl methacrylate (EMA) and butyl acrylate (BA),
The copolymerization ratio (EMA / BA) is 100 to 70/0 to 30 (total component total 100 parts by weight), and the number average molecular weight is 1,000 to 100,000, preferably about 1,000 to 30,000,
And so on.

  Among such (meth) acrylic acid ester-based polymers, preferably a hydrophobic acrylic polymer [(meth) acrylic acid ester content is more than 50% by weight and styrene content is less than 50% by weight], Alternatively, a styrene polymer (with a styrene content of 50% by weight or more) is used, and the (meth) acrylic acid ester polymers of numbering (1) and (2) are particularly preferably used.

  The glass transition temperature (Tg) of such a (meth) acrylic acid ester polymer is preferably 0 ° C. or higher, and particularly preferably 20 to 105 ° C. In addition, in the (meth) acrylic acid ester-based polymer having a low glass transition temperature (Tg) (eg, butyl acrylate (BA) homopolymer), the effect of suppressing cracks in the resulting antifouling coating film may be low. .

  In addition, such a (meth) acrylic acid ester polymer is usually used for 100 parts by weight of the film-forming copolymer in the film-forming copolymer-containing antifouling coating composition containing no chlorinated paraffin. Although used in an amount of 10 to 200 parts by weight, the antifouling coating composition containing this chlorinated paraffin can be further reduced, and 5 to 200 parts by weight with respect to 100 parts by weight of the film-forming copolymer. Can be used.

  That is, in such an antifouling coating composition, zinc oxide is contained in an amount of 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, based on 100 parts by weight of the film-forming copolymer. The (meth) acrylic acid ester polymer is usually contained in an amount of 1 to 200 parts by weight, preferably 5 to 200 parts by weight, more preferably 10 to 200 parts by weight, and particularly preferably 15 to 160 parts by weight. The chlorinated paraffin is desirably contained in an amount of usually 3 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 8 to 100 parts by weight.

  In such an antifouling coating composition, the antifouling agent is usually contained in an amount of 100 to 2000 parts by weight, preferably 150 to 1500 parts by weight, based on 100 parts by weight of the film-forming copolymer. It is desirable that

When the chlorinated paraffin content is in the range of 5 to 150 parts by weight, the effect of suppressing cracks in the obtained antifouling coating film and the mechanical strength of the obtained antifouling coating film are particularly excellent.
In such a (meth) acrylic acid ester-based polymer, as in the case of the film-forming copolymer, if a carboxylic acid residue is present, storage of the resulting antifouling coating composition is possible. In order to significantly reduce the stability, it is desirable that no carboxylic acid residue is present in the (meth) acrylic acid ester polymer, and the acid value (AV value) of the polymer is usually 15 or less, more preferably 10 In the following, it is preferable to use a monomer having no carboxylic acid residue so that it is particularly preferably 5 or less.

  In this antifouling coating composition, for example, even if a coating film (antifouling coating film) made of this antifouling coating composition formed on the ship bottom is submerged, cracks in the antifouling coating film are suppressed and consumed. Control is possible, and a necessary wear level and antifouling performance can be provided according to the environment used.

Therefore, in the antifouling coating composition containing the (meth) acrylic acid ester-based polymer in this way, the film thickness of the antifouling coating film can be reduced to the maximum according to the use. Also excellent.
[Scale pigments]
The antifouling paint composition according to the present invention may contain the following scaly pigments in addition to the above-mentioned film-forming copolymer, the above-mentioned zinc oxide, and the above-mentioned chlorinated paraffin. .

  Examples of the scaly pigment include mica powder, scaly aluminum powder, copper powder, zinc dust, pearl pigment, and the like, and mica powder is preferably used. More specific examples of such raw mica powders include, but are not limited to, white eels such as white peach, red peach, saw down peach, sericite, vanadine peach, illite, black peach, black eel, cinnamon, chinwald peach, etc. In general, celadon stone is used.

The average particle diameter, aspect ratio, and the like of such scaly pigments are not particularly limited, but preferably the average particle diameter is 0.1 to 200 μm, and the aspect ratio is (ratio of long side / short side of particles). ) It is desirable that it is 10 or more.

  In such an antifouling coating composition, zinc oxide is contained in an amount of 1 to 1000 parts by weight, preferably 3 to 500 parts by weight, based on 100 parts by weight of the film-forming copolymer. It is usually contained in an amount of 5 to 65 parts by weight, preferably 8 to 55 parts by weight, and the scaly pigment is usually contained in an amount of 1 to 100 parts by weight, preferably 5 to 90 parts by weight.

  In such an antifouling coating composition, the antifouling agent is usually contained in an amount of 100 to 800 parts by weight, preferably 200 to 600 parts by weight, based on 100 parts by weight of the film-forming copolymer. It is desirable. When the scale pigment is in the range of 1 to 100 parts by weight, it is possible to form an antifouling coating film that is excellent in the additive effect, excellent in the antifouling effect, and particularly excellent in crack resistance.

In general, it is considered that if a scaly pigment is blended in an antifouling paint composition or the like, it is effective in improving the crack resistance of the resulting coating film.
However, in the conventional antifouling paint, when a scaly pigment having no physiological activity is blended, elution of the antifouling agent from the obtained antifouling coating is prevented, and the antifouling effect is greatly reduced. There was a problem with it.

  However, the antifouling coating film formed from the silyl ester antifouling coating composition (AF) excellent in self-polishing property (consumable) as in the present invention has excellent surface renewability in seawater, Even if scaly pigment is present on the surface of the film, it has sufficient renewability of the coating film, and the antifouling activity is originally at a very high level, so excessive elution of the antifouling agent is controlled and kept within an appropriate range. In addition, the occurrence of cracks after submergence can be more efficiently suppressed while (controlling).

The film-forming copolymer is (meth) acrylic acid tributylsilyl ester [TBS (M) A
] And an antifouling coating film composed of an antifouling coating composition that is a copolymer of methyl (meth) acrylate [M (M) A], and more specifically, in seawater, Under the influence of hydroxide ion (OH ⁻ ) or the like, a carbonyl group (—CO—) in which the tributylsiloxy group (Bu ₃ SiO—) in the film-forming copolymer is bonded to the copolymer main chain. ) And becomes tributylsilanol (Bu ₃ SiOH) and dissolves in seawater.

Meanwhile, polymers constituted the main chains of the carboxylic acid salt structure (-COO ^-), the contact surface between the seawater antifouling coating film for going to fall off, dissolved in seawater (antifouling coating film surface) Are considered to be updated one after another.

For this reason, the antifouling agent contained in the antifouling coating film is promptly released from the antifouling coating film surface.
However, when the scaly pigment is contained in the paint as described above, contact between seawater and the antifouling agent and the film-forming copolymer is suppressed. It seems that will be obtained.

  The antifouling paint composition according to the present invention contains the above (meth) acrylic acid ester polymer and scaly pigment in addition to the above-mentioned film-forming copolymer, zinc oxide and chlorinated paraffin. May be.

In such an antifouling paint composition, with respect to 100 parts by weight of the film-forming copolymer,
Zinc oxide is contained in an amount of 1-1000 parts by weight, preferably 3-500 parts by weight, and the chlorinated paraffin is usually 3-200 parts by weight, preferably 5-100 parts by weight, more preferably 10-100 parts by weight. Contained in the amount of parts,
The (meth) acrylic acid ester polymer is usually contained in an amount of 1 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 100 parts by weight,
The scaly pigment is usually contained in an amount of 0.5 to 400 parts by weight, preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight.

In such an antifouling coating composition, the antifouling agent is usually contained in an amount of 100 to 2000 parts by weight, preferably 150 to 1500 parts by weight, based on 100 parts by weight of the film-forming copolymer. It is desirable that
[Dehydrating agent]
In addition, the antifouling coating composition containing a dehydrating agent can further improve the storage stability. Examples of such a dehydrating agent include anhydrous gypsum (CaSO ₄ ), synthetic zeolite-based adsorbent (trade name: Molecular sieves), orthoesters such as methyl orthoformate and methyl orthoacetate, orthoborate esters, silicates and isocyanates (trade name: Additive TI), and the like. Anhydrous gypsum and molecular sieves are preferred, especially molecular sieves. Is preferably used.

Such dehydrating agents can be used alone or in combination of two or more.
The molecular sieve is more preferably used than anhydrous gypsum for the following reasons.

  That is, when an antifouling paint composition containing anhydrous gypsum is applied, water-soluble hydrated gypsum precipitates on the surface of the coating film in the case of sweat or rain after application, causing whitening of the coating film. In addition, when further overcoating the surface of the antifouling coating film, there is a tendency to affect the overcoating property. Therefore, in order to avoid these, it is particularly preferable to use a molecular sieve.

Further, in relation to such a dehydrating agent, the present invention will be described in more detail while comparing with the coating composition described in JP-A-7-18216. Since a relatively low molecular weight copolymer is contained as a functional copolymer, thickening gelation during storage is suppressed to some extent even in an antifouling coating composition not containing the dehydrating agent.

  In addition, even if the antifouling coating composition is somewhat thickened during long-term storage and has a tendency to gel, the antifouling coating composition is diluted with an appropriately selected solvent to If it can be applied, the formed coating film has wearability (self-polishing property) and good antifouling property is recognized.

  Even a coating film formed by applying an antifouling paint composition that has been thickened and gelled in this way has wear characteristics mainly in the amount as described above and a relatively low molecular weight. This is probably because a film-forming copolymer is used.

On the other hand, in the coating composition described in JP-A-7-18216, when no dehydrating agent is blended, a remarkable tendency to thicken and gel is observed during storage of the coating composition. In a coating film formed by applying a coating composition thickened and gelled to the bottom of a ship or the like, wearability is hardly recognized and the antifouling property is poor.

Such a dehydrating agent is usually used in an amount of 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the film-forming copolymer.
[Anti-sagging / anti-settling agent, pigment, etc.]
The anti-sagging / anti-settling agent may be blended in an arbitrary amount other than those that impair the storage stability of the antifouling paint composition such as organic clay.

Such anti-sagging and anti-settling agents include Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonate salts, polyethylene wax, amide wax, hydrogenated castor oil wax system, polyamide wax system. And a mixture of both, synthetic finely divided silica, oxidized polyethylene wax, and the like. Preferably, hydrogenated castor oil wax, polyamide wax, synthetic finely divided silica, and oxidized polyethylene wax are used. Examples of such anti-sagging and anti-settling agents include those marketed under trade names such as “Dispalon 305” and “Dispalon 4200-20” manufactured by Enomoto Kasei Co., Ltd.

  As the pigment, in addition to the scaly pigment (eg, mica powder), various conventionally known organic and inorganic pigments (eg, titanium white, bengara) can be used. Various colorants such as dyes may also be included.

  As the solvent, for example, various solvents such as aliphatic, aromatic (e.g., xylene, toluene, etc.), ketone, ester, ether, and the like that are usually blended in antifouling paints are used.

  The antifouling paint composition as described above is applied to the surface of underwater structures (eg, water supply / drainage ports of nuclear power plants) or to various marine civil engineering facilities such as gulf roads, submarine tunnels, port facilities, canals and waterways. If it is applied to the surface of a sludge diffusion prevention film for construction, or the surface of various molded products such as ships and fishing gear (eg ropes, fishing nets) one or more times according to conventional methods, it will be exposed to dry conditions. Or anti-fouling coating coated hulls or underwater structures with excellent resistance to cracking and stability over time, such as in the vicinity of the waterline where immersion in water and exposure to air are repeated. can get.

  The antifouling paint composition according to the present invention may be applied directly to the surface of the above-mentioned hull or underwater structure, or a hull or underwater structure to which a base material such as a rust preventive or primer has been applied in advance. You may apply | coat to the surface of these.

  Furthermore, the antifouling of the present invention is used for repair on the surface of a hull, underwater structure or the like that has already been coated with a conventional antifouling paint or is coated with the antifouling paint composition of the present invention. The coating composition may be overcoated.

Thus, although the thickness of the antifouling coating film formed on the surface of a hull, an underwater structure, etc. is not specifically limited, For example, it is about 30-150 micrometers / time.
[The invention's effect]
Such an antifouling coating composition according to the present invention is particularly excellent in crack resistance and peeling resistance under drying such as being exposed to air, and is stable over time (that is, repeatedly dried due to fluctuations in the waterline). It is possible to form a coating film that is less likely to change over time and has long-term stability) by being exposed to the bottom or immersed in water.

In particular, in addition to the film-forming copolymer and zinc oxide, the book further contains the chlorinated paraffin, (meth) acrylic acid ester polymer, dehydrating agent, antifouling agent (excluding zinc oxide), etc. In addition to the above effects, the antifouling paint composition of the invention is further excellent in physical properties such as peel resistance to a base material such as a ship bottom or a primer layer, and also excellent in antifouling properties and self-polishing properties (consumability). The antifouling coating film can be formed, and it is excellent in storage stability.
[Example]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

In the following examples and comparative examples, “part” means “part by weight”. In addition, the amount of each component in the table, for example, the amount of copolymer component, the amount of chlorinated paraffin (salt salt), the amount of coloring pigment, cuprous oxide, zinc white, etc., or the amount of solvent (eg, xylene) Unless otherwise indicated, all are indicated by “parts by weight”.
[ Production example of polymer]
(Production of copolymer S-1)
A reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, and a heating / cooling jacket was charged with 100 parts of xylene and heated and stirred at a temperature of 90 ° C. under a nitrogen stream.

While maintaining the same temperature, a mixture of 40 parts of tributylsilyl methacrylate, 60 parts of methyl methacrylate and 1.2 parts of 2,2′-azobisisobutyronitrile as a polymerization initiator was added to the reactor from the dropping device for 4 hours. It was dripped over.

Thereafter, stirring was continued for 4 hours at the same temperature to obtain a colorless and transparent copolymer solution S-1.
The heating residue after heating the obtained copolymer solution S-1 at 105 ° C. for 3 hours was 49.9% by weight, and 95% by weight or more of each monomer was determined from the quantification result of the residual monomer by GPC. Incorporated in the polymer, the polymerization rate change during the reaction is almost the same for each monomer, and each component unit derived from these monomers is considered to be randomly arranged at the ratio of the amount of monomer used. It is done.

The glass transition temperature (Tg) of the copolymer (heating residue) S-1 in the copolymer solution S-1 is 51 ° C., and the viscosity of the copolymer solution S-1 at 25 ° C. is 295 cps. Yes, the number average molecular weight (Mn) by GPC measurement was 11,200, and the weight average molecular weight (Mw) was 21,200.
(Production of Copolymer S-2 to Copolymer S-6)
Copolymer S-2, Copolymer S-3, Copolymer in the same manner as described above except that the dripping components were changed as shown in Table 1 during the production of Copolymer S-1. S-4, copolymer S-5, and copolymer S-6 were obtained, and the physical properties of these copolymers (solutions) were measured in the same manner as described above.

  The results are also shown in Table 1.

  Types and physical properties of compatible (meth) acrylic acid ester polymer component (solution) used in constituting the antifouling coating composition [heating residue (% by weight / polymer solution) and the polymer component The viscosity (Gardner / 25 ° C.), molecular weight (Mn: measured by GPC), acid value (AV), glass transition temperature (Tg ° C.)] of the compatible (meth) acrylic acid ester polymer contained in .

  The results are shown in Table 2.

[Examples 1-31, Comparative Examples 1-7]
[Production example of antifouling paint composition]
Each antifouling coating composition having the composition shown in Tables 4 to 11 was produced (each component amount is expressed in parts by weight).

  When producing the antifouling paint compositions having the composition shown in Tables 4 to 11, these composition components were shaken together in a paint shaker containing glass beads for 2 hours and then aged at room temperature for 12 hours. Went. Next, the mixture was filtered through a 100 mesh filter to obtain a desired antifouling paint composition.

  The viscosities immediately after production (Ku value / 25 ° C.) measured with a Stormer viscometer for the antifouling coating composition and the viscosities after storage for 1 month at room temperature are also shown in Tables 12-14. Further, the antifouling property, the degree of wear over time, the physical properties at alternating wet and dry parts, and the coating strength were evaluated using the antifouling coating composition as follows.

The results are shown in Tables 12-14.
[Evaluation of antifouling properties]
A 70 × 200 × 3 mm sandblast plate that was bent so as to be attached to the side of a rotating drum installed in the seawater of Hiroshima Bay was prepared.

  To this sandblast plate, epoxy zinc rich primer (zinc powder content 80% by weight in dry coating film), tar epoxy anticorrosive paint, vinyl binder coat so that the dry film thicknesses become 20 μm, 150 μm and 50 μm, respectively. Then, the test antifouling paint composition was applied so that the film thickness after drying was 200 μm to obtain a test plate.

  After mounting this test plate on a rotating drum and simulating ship operation for 12 months under a peripheral speed of 15 knots and 50% operating conditions (alternating operation of 12 hours at night and 12 hours during the day), antifouling properties (dynamic Anti-fouling property, adhesion area% of various aquatic organisms to the test plate), and degree of wear μ (thickness reduction: star column in the table) were evaluated.

In addition, the degree of wear over time, the physical properties at alternating wet and dry parts, and the coating strength were also evaluated under the following conditions.
[Evaluation of wear over time]
After coating an epoxy zinc rich primer (with a zinc powder content of 80% in the dry coating film) on a disc-shaped sandblast plate with a diameter of 300 mm and a thickness of 3 mm, the dry film thickness is 20 μm, The tar-epoxy anticorrosion paint was applied so that the dry film thickness was 150 μm, and then left for another day, and further, a vinyl-based binder coat was applied in order so that the dry film thickness was 50 μm. Then, it was dried indoors for 7 days.

Thereafter, a test antifouling coating composition was applied radially in the radial direction using an applicator having a clearance of 500 μm to obtain a test plate. Attach this test plate to a motor in a thermostatic bath containing 25 ° C seawater, rotate at a peripheral speed of 15 knots under 100% operating conditions (continuous operation day and night), and wear rate around the circumference (thickness reduction) ) Was measured 4 times every 3 months.
[Evaluation of physical properties in alternating wet and dry parts]
A 70 mm × 150 mm × 2.3 mm sandblast plate was coated in the same manner as the coating method used in “Evaluation of antifouling properties” to obtain a test plate.

  This test plate is attached to a rotary dry alternating test machine that repeats 12 hours of immersion in seawater and 12 hours of exposure in the air. After the test machine has been operated for 3 months, the physical properties of the test plate are evaluated visually. Went.

The evaluation criteria are as follows.
5: No crack or peeling on the surface of the test plate.
4: A slight crack is recognized on the test plate surface.
3: Fine cracks are observed on the surface of the test plate.
2: Remarkable cracking is observed on the surface of the test plate.
1: Remarkable cracking with peeling is observed on the surface of the test plate.
[Evaluation of coating strength]
After coating tar epoxy anticorrosive paint on a 70mm x 150mm x 2.3mm sandblasting plate so that the dry film thickness is 150µm, leave it for one day, and then add a vinyl binder coat on the surface. It was coated to 50 μm and then dried in a 40 ° C. incubator for 2 days.

Next, a vinyl binder coat was further applied to the surface of the dry film so that the dry film thickness was 50 μm.
On the next day, after coating the test antifouling paint composition so that the dry film thickness was 150 μm, the same antifouling paint composition was applied on the next day with a dry film thickness of 150 μm ( Total dry film thickness of antifouling paint composition: 150 + 150 = 300 μm).

Then, it was dried for 14 days in a constant temperature / humidity chamber with a temperature of 20 ° C. and a humidity of 75%.
A 50 mm × 50 mm polyethylene sheet was placed on the coating film surface of the test plate thus obtained, and a 30 mm × 30 mm simulated board was placed thereon and pressurized with a load of 30 kg / cm ² for 30 minutes. Then, the damage of the coating film was visually evaluated.

  The evaluation criteria are as follows.

The said evaluation result is collectively shown to Tables 12-14.
In addition, the component names in the table are as follows.
(1) “Toyoparax 150” chlorinated paraffin manufactured by Tosoh Corporation, average carbon number: 14.
5. Chlorine content (amount) 50%, viscosity: 12 poise / 25 ° C., specific gravity: 1.25 / 25 ° C.
(2) “Toyoparax A-40” chlorinated paraffin manufactured by Tosoh Corporation, average carbon number: 24.5, chlorine content (amount) 40.5%, viscosity: 18.5 poise / 25 ° C., specific gravity: 1.16 / 25 ° C.
(3) “Toyoparax 270” chlorinated paraffin manufactured by Tosoh Corporation, average carbon number: 12, chlorine content (amount) 70%, viscosity: 4 poise / 80 ° C., specific gravity: 1.50 / 80 ° C.
(4) "Toyoparax A-70" chlorinated paraffin manufactured by Tosoh Corporation, average carbon number: 24.5, chlorine content (amount) 70%, white powder, specific gravity: 1.65 / 25 ° C.
(5) "Molecular sieve 4A" dehydrating agent, Union Showa Co., Ltd., synthetic zeolite powder.
(6) “Dispalon 305” A hydrogenated castor oil-based sagging agent manufactured by Enomoto Kasei Co., Ltd.
(7) "Dispalon 4200-20" Polyethylene oxide anti-settling agent manufactured by Enomoto Kasei Co., Ltd., 2
0% xylene paste.
(8) “Mica Shiratama”: (Yes) (Wakimoto Mica) scaly pigment, average particle size: 15 μm, aspect ratio: 40.

In the table, “chlorinated paraffin (% by weight) (for copolymer)”, “Cu ₂ O (% by weight) (for copolymer, ie, film-forming copolymer, the same applies hereinafter)”, “ZnO ( The calculation method of “weight%) (to copolymer)” and the like is as follows.

For example, in the “antifouling paint composition P-1”, the “content of salt salt (chlorinated paraffin) (% by weight) (to copolymer)” = 30.8 is obtained as follows.
That is, in the “antifouling paint composition P-1”, chlorinated paraffin is blended in an amount of 4 parts by weight, and “copolymer component (solution) S-1” is blended in an amount of 26 parts by weight. In addition, 26 parts by weight of the “copolymer component (solution) S-1” contains 49.9% by weight of the residual residue (copolymer S-1).

  Therefore, in the “antifouling paint composition P-1”, “chlorinated paraffin (% by weight) (to copolymer)” = [4 / {26 × 49.9 / 100}] × 100% = 30.8 (% By weight).

Claims (11)

  It has a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight, a number average molecular weight of 3000 to 20000, a weight average molecular weight of 4000 to 150,000, and a glass transition point of 25 to 25. It comprises a film-forming copolymer having a viscosity (25 ° C., CPS) in a 50% xylene solution of 80 ° C. and 40 to 1000, and zinc oxide, and the zinc oxide is 100 weight by weight of the film-forming copolymer. The antifouling paint composition is contained in an amount of 1 to 1000 parts by weight relative to parts. It has a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight, a number average molecular weight of 3000 to 20000, a weight average molecular weight of 4000 to 150,000, and a glass transition point of 25 to 25. A film-forming copolymer having a viscosity (25 ° C., CPS) of 40 to 1000 in a 50% xylene solution at 80 ° C., zinc oxide, and chlorinated paraffin;
The zinc oxide is contained in an amount of 1 to 1000 parts by weight and the chlorinated paraffin is contained in an amount of 18 to 65 parts by weight with respect to 100 parts by weight of the film-forming copolymer. Antifouling paint composition. It has a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight, a number average molecular weight of 3000 to 20000, a weight average molecular weight of 4000 to 150,000, and a glass transition point of 25 to 25. A film-forming copolymer having a viscosity (25 ° C., CPS) of 40 to 1000 in a 50% xylene solution at 80 ° C., zinc oxide, and a dehydrating agent;
The zinc oxide is contained in an amount of 1 to 1000 parts by weight and the dehydrating agent is contained in an amount of 0.1 to 200 parts by weight with respect to 100 parts by weight of the film-forming copolymer. An antifouling paint composition. It has a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight, a number average molecular weight of 3000 to 20000, a weight average molecular weight of 4000 to 150,000, and a glass transition point of 25 to 25. A film-forming copolymer having a viscosity (25 ° C., CPS) of 40 to 1000 in a 50% xylene solution at 80 ° C., zinc oxide, chlorinated paraffin, and a dehydrating agent;
The zinc oxide is contained in an amount of 1-1000 parts by weight with respect to 100 parts by weight of the film-forming copolymer, the chlorinated paraffin is contained in an amount of 18-65 parts by weight, and the dehydrating agent is 0. .An antifouling paint composition characterized by being contained in an amount of 1 to 200 parts by weight. The antifouling paint according to any one of claims 1 to 4, wherein at least one of the three alkyl groups bonded to the silicon atom of the trialkylsilyl ester has 3 or more carbon atoms. Composition. 5. The antifouling paint composition according to claim 1, wherein the trialkylsilyl ester is tributylsilyl (meth) acrylate. 5. The antifouling paint composition according to claim 2, wherein the chlorinated paraffin has an average carbon number of 8 to 30 and a chlorine content of 35 to 75%. The antifouling paint composition according to any one of claims 1 to 4, further comprising an antifouling agent (excluding zinc oxide). A coating film formed from the antifouling paint composition according to any one of claims 1 to 8. An antifouling method for a hull or an underwater structure, wherein the antifouling paint composition according to any one of claims 1 to 8 is used. A hull or underwater structure, wherein the surface of the hull or underwater structure is coated with a coating film comprising the antifouling paint composition according to any one of claims 1 to 8.