JP6913757B2 - Antifouling composition - Google Patents

Description

The present invention relates to a marine antifouling coating composition, more specifically a marine antifouling coating composition comprising a particular binder and the binder itself. The present invention further relates to kits suitable for the preparation of antifouling coating compositions and surfaces coated with antifouling coating compositions.

The surface submerged in seawater has been polluted by marine organisms such as green and brown algae, barnacles, mussels, and lamellibrachia. For marine structures such as ships, oil platforms and buoys, such pollution is undesirable and has economic consequences. Staining can result in surface biodegradation, increased load, and accelerated corrosion. For ships, fouling increases frictional resistance, causing deceleration and increased fuel consumption. It may also reduce maneuverability.

Also, underwater structures such as rivers, lakes, canals, industrial plants exposed to water environments such as swimming pools, pipes and freshwater storage tanks have similar problems caused by the attachment and growth of organisms. This reduces the amount of work that can be done, resulting in serious financial losses.

Antifouling coatings are used to prevent the colonization and growth of marine life. These coatings generally contain a film-forming binder, along with various components such as pigments, fillers, solvents, bioactive substances and the like.

Until 2003, the most successful antifouling coating system on the market was the tributyltin (TBT) self-polishing copolymer system. These antifouling coating binder systems were linear acrylic copolymers with a tributyltin pendant group. In seawater, the polymer was gradually hydrolyzed to release the effective biocide, tributyltin. Here, the remaining acrylic copolymer containing the carboxylic acid group became sufficiently soluble or dispersible in seawater and was washed away or lost from the coated surface. This self-polishing effect resulted in a controlled release of the bioactive compound in the coating, resulting in excellent antifouling efficiency and a smooth surface, thus reducing frictional resistance.

The 2001 IMO Convention "International Convention on the Management of Harmful Antifouling Systems for Ships" has banned the application of new TBTs, including antifouling coatings, since 2003. And TBT, including antifouling coatings, has been banned on hulls since 2008.

In recent years, as a result of the TBT ban, new antifouling coating systems have been developed and introduced. One broad group of biological antifouling coatings on the market today are self-polishing antifouling coatings that mimic TBT self-polishing copolymer coatings. These antifouling coatings are based on (meth) acrylic copolymers with pendant hydrolyzable groups that are non-biological. The hydrolysis mechanism is the same as in the case of the copolymer containing TBT. This results in the same controlled dissolution of the polymer, thereby resulting in a controlled release of the antifouling compound from the coating film, resulting in performance similar to an antifouling coating system containing TBT. The most successful self-polishing antifouling system today is based on a (meth) acrylic copolymer of silyl ester functional groups. These coating compositions are described, for example, in European Patent Application Publication No. 0646630, European Patent Application Publication No. 0802243, European Patent Application Publication No. 1342756, European Patent Application Publication No. 1479737, Europe. It is described in Patent Application Publication No. 1641862, International Publication No. 00/77102, International Publication No. 03/070832, and International Publication No. 03/080747. The hydrolyzable binder results in continuous renewal of the coating film and efficient release of the biocide on the coated surface, thereby leaving the surface free of organisms.

The antifouling coating system decomposes by hydrolysis of the pendant group on the polymer backbone, resulting in a water erosible polymer. Hydrolysis of the pendant groups on the polymer backbone results in the formation of carboxylates that make the polymer hydrophilic and thereby erosive. A certain amount of hydrolyzable groups is required to obtain sufficient hydrophilicity and erosive polymer after hydrolysis.

Another method of obtaining a water erosive polymer is to introduce a hydrolyzable group into the polymer backbone, resulting in decomposition of the polymer structure and erosion of the polymer film or coating film. Polyanhydrides are a class of polymers that decompose by hydrolysis of the skeleton. Polyanhydrides are well documented for their surface decomposition properties. Surface decomposition is one of the most important factors in obtaining a successful antifouling coating. The use of certain aromatic polyanhydrides as binders in antifouling coating compositions is described, for example, in WO 2004/096927.

However, the anhydride groups are so unstable in the presence of moisture that it is difficult to design a polyanhydride-based coating system that exhibits slow and controlled hydrolysis for use in antifouling coatings. Is. Therefore, polyanhydrides for antifouling coating compositions generally have a high content of aromatic units to control hydrolysis.

In recent years, polyoxalate has emerged as a class of polymers that are well suited for use as binders in antifouling coatings. The hydrolysis of the skeleton in these compounds is more controlled than in the case of polyanhydrides.

The use of self-polishing binders in which the polymer backbone hydrolyzes in seawater makes it possible to obtain erosive crosslinked polymers and high molecular weight polymers.

An alternative to antifouling coatings (which necessarily contain biocides) is so-called fouling release coatings. These coatings have low surface tension and low modulus and function by providing a "non-adhesive" surface where marine organisms cannot or, if attached, are washed away by the movement of water over the surface. The coating is often based on polysiloxane / silicone / polydimethylsiloxane (PDMS), which generally has very low toxicity. The fouling release system has drawbacks. For example, when applied to the hull, the accumulation of marine life is reduced, but relatively fast ship speeds are required to remove all types of fouling. Therefore, in some cases, it has been shown that it is necessary to navigate at a speed of at least 14 knots for effective release from such polymer-treated hulls.

However, such "non-adhesive" coatings do not show good resistance to soft stains such as mucus and algae over time. In order to overcome this problem, WO 2011/076856 proposes to add a biocide to such a PDMS coating in combination with a hydrophilic modified PDMS oil. WO 2013/00479 relies on the same principle of biocide addition, where the hydrophilic modified polysiloxane moiety is covalently attached to the polysiloxane binder.

However, these mixed materials have limited commercial success because the biocide diffuses too quickly onto the surface at the beginning of the coating life, after which diffusion ceases as the coating ages. More recently, Azemar discusses hybrid coatings based on triblock copolymers of polycaprolactone and PDMS in Progress in Organic coatings, Vol. 87, 2015, pp. 10-19. The PDMS block is copolymerized with caprolactone to give a polycaprolactone polymer block at each end of the PDMS block. Therefore, the polymer contains only one PDMS block with two polyester blocks formed from caprolactone. That is, any hydrolysis occurs only at the ends of the molecule, not at the center of the chain. As we claim, poly (caprolactone units) cannot be used in the production of copolymers because it does not contain two identical functional groups.

International Publication No. 2004/085560 discloses that a polysilyl ester is formed by a reaction of a dicarboxylic acid with an acyloxysilyl compound. The resulting polymer has been proposed for use as a binder for antifouling coatings. However, the claimed polymer always contains the characteristic silyl ester Si-O-CO-link in the backbone. Cyril esters are highly reactive to water and are known to completely decompose within days or weeks. The compounds of WO 2004/08560 are so unstable that they cannot be successfully used in long-term antifouling coating compositions that need to be used for many years. We also observe that the process of making these silyl ester polymers is complex. Our solution uses a much simpler process and avoids problems related to, for example, acid distillation.

WO 2015/082397 teaches coating compositions containing binders formed from the reaction of polysiloxanes with lactones. This results in a polymer chain containing the -CO-alkylene-O- group. This is achieved by ring opening of the lactone. In addition, this polymerization results in a block copolymer because the ring-opening lactone can react with other lactones to prolong the polymerization. Therefore, the polymer is a triblock polymer of structure AAABBBAAA. A relatively high organic to siloxane ratio is required to obtain a curable polymer. This process results in a polymer with a much higher glass transition compared to conventional polysiloxane. This limits the non-adhesiveness, softness, and release potential of the polymer.

European Patent Application Publication No. 0646630 European Patent Application Publication No. 0802243 European Patent Application Publication No. 1342756 European Patent Application Publication No. 1479737 European Patent Application Publication No. 1641862 International Publication No. 00/77102 International Publication No. 03/070832 International Publication No. 03/08847 International Publication No. 2004/096927 International Publication No. 2011/076856 International Publication No. 2013/00479 International Publication No. 2004/085560 International Publication No. 2015/082397

Azemar, Progress in Organic coatings 87, 2015, 10-19

In particular, there remains a problem to be solved regarding the fouling release coating performance over time.

We have recognized that it would be beneficial to have a reproducible fouling release coated surface. The use of renewable surfaces means the physical removal of mucus / algae and other soft stains with or without the need for biocides. Therefore, it would be useful if the fouling release coating composition could provide a renewable surface like that of the antifouling coating composition. This can be achieved with or without the addition of biocides. Biocides can be used when a substrate, such as a hull, can be exposed to slow or severe fouling conditions.

An object of the present invention is to provide a novel binder for a coating composition capable of preventing both animals such as marine organisms, barnacles and algae / mucus from adhering to the surface of aquatic structures such as hulls. .. The idea of the present invention is to combine the advantages of a fouling release coating with a self-polishing antifouling coating, especially to provide a renewable non-adhesive surface on the substrate. The binder may or may not be accompanied by a biocide to potentially extend the antifouling effect of the coating.

Therefore, the present invention combines the advantages of the two techniques to provide a low surface tension renewable coating, optionally with a biocide.

The present invention achieves this object by using a copolymer produced by polymerizing a polysiloxane unit with a shorter comonomer molecule that is not a polysiloxane, and comprises a polymer containing a hydrolyzable ester unit in its skeleton. offer. The binder is formed by copolymerizing a monomer unit containing a thiol group with a vinyl group or a monomer unit containing a thiol with which the thiol group can react. Alternatively, the binder is formed by copolymerization of a monomer unit containing an amine group and a monomer unit containing a vinyl group with which the amine group can react.

We are surprisingly aware that the polymers designed herein hydrolyze in seawater to renew the surface, allowing the leaching of all biocides in the coating as needed. I found that. In addition, the binder of the present invention provides a coating composition having low VOC, low surface energy and low elastic modulus.

Therefore, from one aspect, the present invention is a binder for a coating composition, particularly a marine coating composition, wherein the binder is a polysiloxane group, a plurality of ester groups, and a plurality of thio groups (eg, formula-(eg, formula-(for example). A binder containing a polymer containing a CS-CH ₂ ), for _{example-(CH 2-} S-CH ₂ )), an amino group or a disulfide group SS is provided.

Seen from another aspect, the present invention is a binder for a coating composition, wherein the binder comprises a polysiloxane group, a plurality of ester groups, and a plurality of thio groups, amino groups or disulfide groups in its skeleton. A binder containing a polymer is provided.
In particular, the present invention is a binder for a coating composition, wherein the binder has a plurality of polydimethylsiloxane groups, a plurality of ester groups, and a plurality of thio groups (for example, the formula- (CS-CH _2). )-, For _{example-(represented by CH 2-} S-CH ₂ )-), an amino group (eg, represented by the formula CH _2- NRa-CH _2- ) or SS (where Ra is , H or C _1-6 alkyl groups).

In particular, the present invention is a binder for a coating composition, wherein the binder contains a plurality of polydimethylsiloxane groups, a plurality of ester groups, and a plurality of thio groups (for example, the _{formula- (CH 2-} NR). Provided are binders for coating compositions containing polymers comprising those represented by _a −CH _{2 −), repeating units containing amino or SS groups).}

From another aspect, the present invention provides a binder for a coating composition comprising a reaction product of a vinyl-terminated polysiloxane polyester monomer and a bisthiol monomer or a bisaminomonomer.

From another aspect, the present invention provides a binder for a coating composition containing a reaction product of a thiol-terminated polysiloxane monomer and a vinyl-terminated polyester monomer.

From another aspect, the present invention provides a binder for a coating composition containing a reaction product of a vinyl-terminated polysiloxane monomer and a thiol-terminated polyester monomer.

In another aspect, the present invention provides a binder for a coating composition comprising a reaction product of a vinyl-terminated polysiloxane polyester monomer and a thiol-terminated polyester monomer or an amino-terminated polyester monomer.

From another aspect, the present invention provides a binder for a coating composition containing a reaction product of a thiol-terminated polysiloxane monomer and a thiol-terminated polyester monomer.

From another aspect, the present invention provides a binder for a coating composition comprising a reaction product of a thiol-terminated polysiloxane polyester monomer and a thiol-terminated monomer.

From another aspect, the present invention provides a binder for a coating composition containing a reaction product of a thiol-terminated polysiloxane polyester monomer and a thiol-terminated polyester monomer.

From another aspect, the present invention provides a binder for a coating composition containing a reaction product of an amino-terminal polysiloxane monomer and a vinyl-terminal polyester monomer.

In any of the above monomers, the polyester is preferably a diester.

In a particularly preferred embodiment, the polymer is a reaction product of a (meth) acryloxyalkyl-terminated polysiloxane monomer with a bisthiol monomer such as a thiol-terminated polyester monomer or bisaminomonomer.

In a particularly preferred embodiment, the polymer is a reaction product of a thiol-functionalized polysiloxane monomer and a vinyl-terminated polyester monomer.

In a particularly preferred embodiment, the polymer is a reaction product of a vinyl-terminated polysiloxane monomer and a thiol-terminated polyester monomer.

In a particularly preferred embodiment, the polymer is a reaction product of a thiol-functionalized polysiloxane monomer and a thiol-terminated polyester polyol monomer.

Seen from another aspect, the present invention describes the general formula (A1) or (A2):

(In the formula, each R ₁ is the same or different, unsubstituted or substituted C _1-20 alkyl group, C _2-20 alkenyl group, C _3-20 cycloalkyl group, C _6-20 aryl group, C _7-20. Represents an arylalkyl group, or a polyoxyalkylene chain, especially a methyl group;
X and Y may be the same or different, −CR = CH ₂ − (CR ” ₂ ) x'−CR = CH ₂ , − (CR” ₂ ) _{x ′} −CR ” ₂ −OCO− _{CR = CH 2, -CR "2} -OCO-CR = CH 2, - (CR" 2) x '-SH, - (CR "2) x' -O- (CR" 2) x '-SH, - (CR " ₂ ) _x- [O- (CR" ₂ ) _x' ] _f- OCO-CR = CH ₂ ,-(CR " ₂ ) _x' -(OR ⁸ ) _a- (OR ⁸ ) _b- OR ⁷ _{-SH, - (CR "2)} x '- (OR 8) a - (OR 8) b -OR 7 -CR = CH 2, -CR" 2 -Ar-CR "2 -SH, - (CR" 2 _{) x 'C≡CH, - (CR} "2) x' -O- (CR" 2) x '- (CHOH) - (CR "2) x -OCO-CR = CH 2 or, - (CR" _{2 ^{) x '- (OR 8)}} a - ( represents OR ⁸⁾ _b -OR ⁷ C≡CH;
"R" is independently a C _1-6 alkyl group or H, especially H;
x'is from 1 to 10, for example 1 to 5, especially 2 to 5, especially 3 to 5;
Each R is independently H or Me;
Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, a = 0 to 50, b = 0 to 50, and a + b = 1 to 50;
f is 1 to 50;
Ar is a C _6-12 aryl group; and n is 1 to 500, more preferably 10 to 300, especially 15 to 100;
Alternatively, n'+ m is 1 to 500 in total, more preferably 10 to 300, and particularly 15 to 100. ) With at least one polysiloxane monomer A';
Formula BI
HS-Q3-SH (BI)
(In the formula, Q3 is C2-20 alkyl group, C3-20 cycloalkyl group, phenyl group, biphenyl group, terphenyl group, C7-20 alkylaryl group, alkyl-polysiloxane-alkyl, C4-20 alkylcycloalkyl. Group or polyether;
Here, the C2-20 alkyl group, C3-20 cycloalkyl group, C7-20 alkylaryl group, or C4-20 alkylcycloalkyl group is one or more, for example, O, N, S or P of 1 to 4, for example. Any heteroatom preferably selected from O;
However, the SH group in the monomer B'reacts with the X and Y groups of the ester containing the monomer A'to form the group C—S—CH ₂ or SS group. ) At least one second monomer B';
Or formula (BII) or (BIII):

(Wherein, Q1 is a covalent bond, C1-20 alkyl, C3-10 cycloalkyl, C3-10 cycloalkenyl group, C6-10 aryl group, C7-12 arylalkyl group, wherein R ⁷ - (OR ⁸ ) _{Represents a-} (OR ⁸ ) _b- OR ⁷ polyoxyalkylene chain, Ph- _{OC 1-6} alkyl-OPh-, heterocyclyl group or C4-10 alkylcycloalkyl group;
Here, the C1-20 alkyl group, C3-10 cycloalkyl group, or C3-10 cycloalkenyl group is a hetero selected from 1 or more, for example, 1 to 4 O, N, S or P, preferably O. Arbitrarily containing atoms;
L is a heteroatom selected from 1 or more, eg 1 to 4 O, N, S or P, preferably O or N, or the formula:
− (OR ⁸ ) _a − (OR ⁸ ) _b − OR ^{7 −}
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, and a = 0 to 50, b = 0 to 50 and a + b = 1 to 50, respectively). It is a chain;
R is H or Me;
Q2 is a covalent bond, a C1-20 alkyl group, a C3-10 cycloalkyl group, a C2-6 aminoglycol, a C2-6 thioglycol, or a C6-10 aryl group, wherein the C1-20 alkyl group, said. The C3-10 cycloalkyl group, or C3-10 cycloalkenyl group, optionally comprises one or more heteroatoms selected from, for example, 1 to 4 O, N, S, or P, preferably O;
W and Z are each _{-SH, - (CR "2)} x 'SH, CH 2 = CR-, CH 2 = CR- (CR" 2) x' -, - C≡CH, -NHCH 2 -CR = CH ₂ , NHCH _2- CR≡CH-NHRa, -NHRa, or W and Z = CH ₂ (thus forming a double bond with the C atom to which W / Z is attached). ;
Ra is an H or C1-6 alkyl group, wherein the alkyl group optionally comprises one or more, eg, 1 to 4 O, N, S or P, preferably a heteroatom selected from O. ;
"R" is independently a C _1-6 alkyl group or H, especially H;
x'is from 1 to 10, for example 1 to 5, especially 2 to 5, especially 3 to 5;
However, the W and Z groups in the monomer B'react with the X and Y groups in the monomer A'to form _two C—S—CH groups, an amino group or an SS group. )
At least one second monomer B';
Or formula:
HRaN-Q5-NHRa (DI)
(In the formula, Q5 is a C2-20 alkyl group, a C2-20 alkenyl group, a C3-20 cycloalkyl group, a phenyl group, a biphenyl group, a terphenyl group, Ph-O-Ph, a C7-20 alkylaryl group, an alkyl. -Polysiloxane-alkyl, C4-20 alkylcycloalkyl group, C3-10 heterocyclic group or polyether (eg-(CH ₂ ) ₃ O- (CH ₂ CH ₂ O) _r (CH (CH ₃ ) CH ₂ O) ) _S (CH ₂ ) _3- (where r + s is 1 to 100)), where the C2-20 alkyl group, C3-20 cycloalkyl group, C7-20 alkylaryl group, or C4-20 Alkylcycloalkyl groups optionally contain one or more heteroatoms selected from, for example, 1 to 4 O, N, S or P, preferably O;
Ra is an H or C1-6 alkyl group;
However, the NRaH group in the monomer D'reacts with the X and Y groups in the ester containing the monomer A'to form the group C-NRa-CH _2- . ) Provided a binder for a coating composition such as a marine coating composition containing a reaction product with at least one second monomer D'.

Seen from another aspect, the present invention
General formulas (C1) to (C2):

(In the formula, each R ₁ is the same or different, unsubstituted or substituted C _1-20 alkyl group, C _2-20 alkenyl group, C _3-20 cycloalkyl group, C _6-20 aryl group, C _7-20. Represents an arylalkyl group, or polyoxyalkylene chain;
X and Y may be different even in the _{same, - (CR "2) x} '-NRaH, - (CR" 2) x' -NH- (CR "2) x '-NRaH, - ( _{CR "2) x '-O- (} C1-6 _{alkyl) x' -NRaH, - (CR} " 2) x '- (O-C2-6 _{alkyl) x' -NRaH, - (CR} "2) x ' _{-O- (CR "2) x '} -NRaH or -CR," ₂ -Ar-CR "represents ₂ -NRaH;
"R" is independently a C _1-6 alkyl group or H, especially H;
Ra is an H or C _1-6 alkyl group;
x'is 1 to 10, for example 1 to 5, especially 2 to 5, especially 3 to 5, and n is 1 to 500, more preferably 10 to 300, especially 15 to 100;
Alternatively, n'+ m is 1 to 500 in total, more preferably 10 to 300, and particularly 15 to 100. ) With at least one polysiloxane monomer C';
Equation (BX) or (BXI)

(Wherein, Q1 is a covalent bond, C1-20 alkyl, C3-10 cycloalkyl, C3-10 cycloalkenyl group, C6-10 aryl group, C7-12 arylalkyl group, wherein R ⁷ - (OR ⁸ ) _{Represents a-} (OR ⁸ ) _b- OR ⁷ polyoxyalkylene chain, -Ph- _{OC 1-6} alkyl-OPh-, heterocyclyl group or C4-10 alkylcycloalkyl group;
Here, the C1-20 alkyl group, C3-10 cycloalkyl group, or C3-10 cycloalkenyl group is a hetero selected from 1 or more, for example, 1 to 4 O, N, S or P, preferably O. Arbitrarily containing atoms;
L is a C1-20 alkylene group, or formula:
− (OR ⁸ ) _a − (OR ⁸ ) _b − OR ^{7 −}
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, respectively, and a = 0 to 50, b = 0 to 50, and a + b = 1 to 50.)
Is a polyoxyalkylene chain of
R is H or Me;
Q2 is a covalent bond, a C1-20 alkyl group, a C3-10 cycloalkyl group, a C2-6 aminoglycol, a C2-6 thioglycol, or a C6-10 aryl group, wherein the C1-20 alkyl group, said. The C3-10 cycloalkyl group, C3-10 cycloalkenyl group optionally comprises one or more, for example 1 to 4, heteroatoms selected from O, N, S, or P, preferably O;
W and Z are CH ₂ = CR-, CH ₂ = CR-CH _2- , -C≡CH, or W and Z are = CH ₂ (thus with the C atom to which W / Z is bonded). (Forms a double bond);
However, the W and Z groups in the monomer B'react with the amino X and Y groups in the monomer C'to form the C-NRa-CH _2- group. ) Provided a binder for a coating composition containing a reaction product with at least one second monomer B'.

In another aspect, the invention releases fouling, preferably in the absence of a biocide, comprising the binder as defined above and at least one of a filler, a pigment, a solvent, an additive, a curing agent and a catalyst. A coating composition is provided.

From another aspect, the present invention provides a fouling release coating composition comprising the binder and antifouling agent as defined above.

Seen from another aspect, the present invention provides a method of protecting an object from fouling, comprising the step of coating at least a portion of the object to be contaminated with the coating composition, and preferably the step of curing the composition. offer.

Seen from another aspect, the present invention provides an object coated with the coating composition as defined above, preferably a cured composition.

Seen from another aspect, the invention is defined herein as a polysiloxane unit A'so that a hydrolyzable ester functional group is present in the skeleton of the copolymer to form a -ABAB- copolymer. Provided is a method for preparing a binder for a marine coating composition, which comprises a step of copolymerizing with at least one second monomer B'of.

In another aspect, the present invention provides the use of the binder as defined above for use in a fouling release composition or a marine antifouling coating composition.

[Definition]
The terms biocide and antifouling agent are used interchangeably herein and are defined below. The term (meth) means any presence of a methyl group.

The binder of the present invention contains a plurality of ester hydrolyzable groups in the skeleton of the molecule. Ester hydrolyzable functional groups are groups that are hydrolyzed in seawater. The polymer should preferably contain more than one, eg, 3 or more hydrolyzable ester groups in the backbone of the polymer. Other hydrolyzable groups may also be present.

It will be appreciated that the rate of the hydrolysis reaction is highly dependent on the chemical structure / composition of the compound / binder and the surrounding environmental conditions (salt, pH, temperature, water content, etc.). The hydrolyzable group must be a group that hydrolyzes at a temperature of 0 ° C to 35 ° C and at a pH and salt content that reflects natural seawater.

The ester "hydrolyzable group" undergoes a hydrolysis reaction at a rate sufficient to cause the polishing effect of the coated surface as the surface moves in seawater, i.e. in the temperature range of 0 ° C to 35 ° C. It must be a group that is hydrolyzed in seawater and at a pH and salt content that reflects natural seawater.

For the avoidance of doubt, ethers, thioethers, amides and amines are not considered hydrolyzable. Siloxane groups are not considered hydrolyzable.

The ester hydrolyzable group must be present in the backbone of the polymer. Ester hydrolyzable groups repeat in the backbone. Hydrolyzable groups must be present in the backbone of the polymer, while hydrolyzable groups can be present in the side chains of the polymer.

To be effective, the ester hydrolyzable group must spread, for example, not only at the ends of the molecule, but throughout the polymer molecule. The copolymer of the present invention is preferably not a block copolymer in which a block of polysiloxane and a terminal block of another material such as polyester are present, that is, a polymer having a structure AAAABBBBBBAAAA. Rather, the copolymers of the invention preferably have a structure having at least two repeating units of monomer A'(or C') and at least two repeating units of monomer B'(or D', etc.)-[ABAB]. -. It will be appreciated that there may be many repeating units and that the formula [ABAB]-is intended to include copolymers containing any number of AB repeating units. The molecular weight is defined below.

Monomers A'and B'(or A'and D'or C'and B', etc.) react together to form polymer repeating units A and B (or AD, etc.). Usually, the linker group formed is a thiolinker of formula-(CS-CH _{2 )-such as (CH 2-} S-CH _2)-. Therefore, the thio group in the skeleton of the polymer means the presence of thioether. The linker can also be an amino linker, for example C-NRa-CH _2- . The formula- (CS-CH ₂ ) allows the first C to be attached to one or two hydrogens or one or two carbon atoms or a mixture of C and H. For example, when using 1,4-benzenedithiol, the S atom will bond to _{CH 2 from the C and vinyl groups of the benzene ring.} The − (C—S—CH ₂ ) − C atom can be double bonded to the adjacent C in the chain, such as −C = CH−S—CH _{2−. The two} C-NRa-CH groups allow the first C to bond to one or two hydrogens or one or two carbon atoms or a mixture of C and H.

When the two monomers terminate in a thiol, a disulfide is formed. Such disulfides are likely to be random copolymers of monomers. It is understood that when one monomer contains bisthiol functionality, disulfide formation is avoided by using reaction conditions / catalysts that promote the desired monomer reaction, eg radical initiation promotes the thiol-ene reaction. Will be done.

It will be important that the combination of monomers used forms a polymer containing ester groups in the backbone of the polymer. Therefore, if the monomer B'or D'does not contain an ester group, the monomer A'or C'must contain an ester group and vice versa. Therefore, the monomers BI and DI need to react with the ester containing the monomer A'. One of ordinary skill in the art can identify the X, Y, W and Z groups that will react to form the defined linker.

In any embodiment of the invention, the alkyl or alkylene group is preferably linear.

Both n'and m have a value of 0 to 500, for example n'+ m, in addition having a value of 1 to 500, more preferably 10 to 300, particularly 15 to 100.

As used herein, the term arylalkyl groups, binding bind benzylic linker (CH ₂ -Ph) via an alkyl moiety is used to also cover methylphenyl type group via an aryl group.

The vinyl-terminated monomer, amine-terminated monomer or thiol-terminated monomer means that the terminal groups on the monomer are vinyl (CH = CH ₂ or CR = CH ₂ ), amino-NRaH or thiol (SH), respectively. It will be appreciated that all monomers must contain at least two such groups. Preferably, the vinyl-terminated monomer is terminated with a methacryloxy group, particularly a (meth) acryloxyalkyl group.

As used herein, the term polyester is used to refer to a monomeric unit that contains multiple ester groups in the backbone of the molecule. The preferred monomer unit is based on the diester as a polyester. Preferably, the polyester monomer is a diester monomer. Monomers containing two metharoxy groups include two esters.

The present invention relates to coating compositions, especially novel binders for marine coating compositions. The new binder can be used in a fouling release coating composition or an antifouling coating composition. The fouling release composition is preferably free of antifouling agents and is ideally formed from a coating composition containing the binder of the invention by cross-linking the composition. The term antifouling coating composition refers to a composition comprising the binder of the present invention and at least one marine antifouling agent. Due to the fact that the binder contains ester hydrolyzable groups, the binder can be used for any type of coating. Slow hydrolysis also allows the coated surface to regenerate. This regeneration effectively addresses the problem of algae / mucus formation on the fouling release coating composition. The hydrolysis reaction allows for a controlled release of the antifouling agent in the antifouling coating.

The term coating composition is used below to refer to either an antifouling coating composition or a fouling release coating composition.

The term binder is a term of the present technology. The binder is the actual film-forming component of the coating composition. The coating composition comprises a binder as well as other ingredients, as described in detail below. The binder imparts adhesiveness and binds the components of the coating composition together.

The polymer binder of the present invention is composed of a plurality of monomers, for example, at least two monomers. In the first embodiment, a copolymer having at least one polysiloxane unit A'(which can be regarded as a polysiloxane monomer) reacts with the polysiloxane unit A to have a plurality of ester hydrolyzable bonds in the polymer skeleton. There is at least one other monomer unit (referred to herein as a second monomer) B'or D'that produces. The polymer backbone ideally comprises a group- [CH _2- S-CH ₂ -]-as well as a plurality of -COO- (or (OCO)) groups. The ester functional group can be derived from monomer A'and / or monomer B'.

The polymer is preferably type-ABABA-because it is formed by addition polymerization and is not a block copolymer of type AAABBBBBBBAAA. It is ester hydrolyzability that hydrolyzes over time in seawater, allowing the surface of the fouling release coating to regenerate and allowing the biocide present in the antifouling composition of the present invention to be renewed and leached. It is a bond.

The skeleton contains a hydrolyzable bond-O-CO-. Other hydrolyzable bonds may be present, but preferably the only hydrolyzable linker present is an ester group. Since the hydrolyzable bond is present in the skeleton of the polymerization unit before polymerization, it can become a part of the skeleton of the copolymer during polymerization. Monomer A'or B'contains at least one ester hydrolyzable group within the backbone of the monomer and will become part of the polymer backbone by copolymerization.

It will be appreciated that the polysiloxane unit may act as a nucleophile or as an electrophile, depending on the functional groups present. Although it may be easy to use a polysiloxane unit as a nucleophile, the present invention places an electrophile at the end of the polysiloxane unit, allowing a second monomer to attack the polysiloxane unit. Can be easily adapted. The polymerization is preferably addition polymerization, but other types of polymerization well known to those of skill in the art can also be used.

The core of the present invention is the recognition that valuable marine binders can be prepared by introducing hydrolyzable bonds such as -O-CO- into the backbone of polysiloxane polymers. As used herein, this is achieved with monomers functionalized to have thiol and vinyl end groups that extend disulfide or thiol bonds in the polymer. Alternatively, the monomer has a vinyl-terminal group and an amino-terminal group that extend the amino bond in the polymer.

In either embodiment, preferably one of the monomers A'or B'contains two ester groups.

The polysiloxane unit copolymerized to produce the binder of the present invention preferably has the general formula (A1):

(In the formula, each R ₁ is the same or different, unsubstituted or substituted C _1-20 alkyl group, C _2-20 alkenyl group, C _3-20 cycloalkyl group, C _6-20 aryl group, C _7-20. Represents an arylalkyl group, or polyoxyalkylene chain;
X and Y may be different even in the _{same, -CR = CH 2, - (} CR "2) x '-CR = CH 2, - (CR" 2) x' -CR "2 -OCO _{-CR = CH 2, -CR "2} -OCO-CR = CH 2, - (CR" 2) x '-SH, - (CR "2) x' -O- (CR" 2) x '-SH, − (CR ” ₂ ) _x − [O − (CR” ₂ ) _x' ] _f −OCO −CR = CH ₂ , − (CR ” ₂ ) _x'− (OR ⁸ ) _a − (OR ⁸ ) _{b − OR ^{7 -SH, - (CR "2}} ) x '- (OR 8) a - (OR 8) b -OR 7 -CR = CH 2, -CR" 2 -Ar-CR "2 -SH, - (CR" _{2) x 'C≡CH, - (} CR "2) x' -O- (CR" 2) x '- (CHOH) - (CR "2) x -OCO-CR = CH 2 or - (CR" _{2 ^{) x '- (OR 8)}} a - ( represents OR ⁸⁾ _b -OR ⁷ C≡CH;
"R" is independently a C _1-6 alkyl group or H, especially H;
x'is from 1 to 10, for example 1 to 5, especially 2 to 5, especially 3 to 5;
Each R is independently H or Me;
Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, a = 0 to 50, b = 0 to 50, and a + b = 1 to 50;
f is 1 to 50;
Ar is a C6-12 aryl group; and n is 1 to 500, more preferably 10 to 300, especially 15 to 100. ).

Preferably, R ₁ is a C1-6 alkyl group, especially Me. Therefore, polydimethylsiloxane (PDMS) is preferably used.

In one embodiment, the monomer A'is of formula A4.

(In the formula, the substituent is as defined above, Q4 is (meth) acrylate, and a = 0 to 50).

In monomer A', preferably X and Y may be the same or different. Preferably, X and _{Y, -CR = CH 2, - (} CH 2) x '-CR = CH 2, - (CH 2) x' -CH 2 -OCO-CR = CH 2, -CH 2 -OCO _{-CR = CH 2, - (CH} 2) x '-SH, - (CH 2) x' -O- (CH 2) x '-SH, - (CH 2) x' -O- (CH 2) x _{'-OCO-CR = CH 2,} - (CH 2) x' - (OR 8) a - (OR 8) b -OR 7 -SH, - (CH 2) x '- (OR 8) a - (OR ^{_{8) b -OR 7 -CR = CH}} 2, -CH 2 -Ar-CH 2 -SH, - (CH 2) x '-C≡CH, - (CH 2) x' -O- (CH 2) x _' -(CHOH)-(CH ₂ ) _x -OCO-CR = CH ₂ or -C≡CH.

More preferably, in monomer A', X and Y are −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH ₂ −OCO −CR = CH _{2 , -CH 2 -OCO-CR = CH} 2, - (CH 2) x '-O- (CH 2) x' - (CHOH) - (CH 2) x -OCO-CR = CH 2 or - (CH ₂ ) _x 'represents the -SH.

Particularly preferably, in monomer A', X and Y are −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH ₂ −OCO−CH = CH _{2 , -CH 2 -OCO, -CH = CH} 2, - (CH 2) x '-CH 2 -OCO-CMe = CH 2, -CH 2 -OCO-CMe = CH 2, - (CH 2) x' - It represents SH or − (CH ₂ ) ₃ −O− (CH ₂ ) − (CHOH) − (CH ₂ ) −OCO-CR = CH ₂ .

Particularly preferably, in monomer A', X and Y are −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH ₂ −OCO−CH = CH _{2 , -CH 2 -OCO-, CH = CH} 2, - (CH 2) x '-CH 2 -OCO-CMe = CH 2, -CH 2 -OCO-CMe = CH 2, - (CH 2) x' - It represents SH or − (CH ₂ ) ₃ −O− (CH ₂ ) − (CHOH) − (CH ₂ ) −OCO-CR = CH ₂ (where x'is 1 to 5).

Preferably, all R ₁ groups are the same. Preferably, R ₁ is a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _6-20 aryl group, or a C _7-20 aryl alkyl group. Preferably, R ₁ is unsubstituted. Preferably, R _{1 is a C 1-6} alkyl group, such as an ethyl group or especially a methyl group. Therefore, PDMS is particularly preferably used. However, it is also possible that at least one R ₁ group is a polyoxyalkylene chain. The molecule is likely to contain multiple of these groups distributed in the polysiloxane backbone. The presence of such chains enhances the hydrophilicity of the molecule. A suitable polyoxyalkylene chain is of the formula:
R ⁷ − (OR ⁸ ) _a − (OR ⁸ ) _b ^{− OR 9}
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, and R ⁹ is H, CH ₃ CO-, CH ₃ CH ₂ CO-, HCO-, or C _1-6. It is an alkyl group and can be one of a = 0 to 50, b = 0 to 50 and a + b = 1 to 50). ^{Preferably, R 9} is not H to avoid all side chain reactions. R ⁹ is preferably a CH ₃ CO-, CH ₃ CH ₂ CO-, HCO-, or C _1-6 alkyl group, particularly CH ₃ CO- or CH ₃ CH ₂ CO-.

Therefore, suitable materials include those selected from polyoxyethylene, polyoxypropylene, and poly (oxyethylene-co-oxypropylene).
Preferred polysiloxane monomers are based on polydimethylsiloxane (PDMS).

The end groups X and Y are preferably the same.

Preferably, all R "groups are the same. Preferably, R" is H.

Particularly preferably, in monomer A', X and / or Y are −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH ₂ −OCO−CH = _{CH 2, -CH 2 -, OCO} -CH = CH 2, - (CH 2) x '-CH 2 -OCO-CMe = CH 2, -CH 2 -OCO-CMe = CH 2 , or, - (CH _{2) x} 'is -SH. Particularly preferably, in monomer A', X and Y are (meth) acryloxipropyl.

In a preferred option, the number average molecular weight (Mn) of the polysiloxane monomer A'can be at least 700, such as at least 1200, such as at least 2000. An upper limit of 40,000, such as an upper limit of 20,000, such as an upper limit of 17,000, such as an upper limit of 15,000, is appropriate.

Theoretically, branched polysiloxane monomers can be used, and therefore there are more terminal groups than just the X and Y specified in formula (A') above. The use of the branched structure allows the formation of a branched copolymer with the second monomer. However, the use of bifunctional polysiloxanes that contain essentially two reactive end groups is considered preferred as such monomers allow the formation of essentially linear polymers. Any polymer of the present invention contains at least two residues derived from polysiloxane units.

Therefore, the preferred polysiloxane monomer A'is of formula (A5):

(Wherein, X and Y are the _{same, -CH = CH 2, - (} CH 2) x '-CH = CH 2, - (CH 2) x' -CH 2 -OCO-CH = CH 2, _{-CH 2 -OCO-CH = CH 2} , - (CH 2) x '-CH 2 -OCO-CMe = CH 2, -CH 2 -OCO-CMe = CH 2, - (CH 2) x' -O- _{(CH 2) x '- (} CHOH) - (CH 2) x -OCO-CR = CH 2 or - (CH _{2) x'} represents -SH;
x'is 1 to 10, especially 2 to 5, for example 3 to 5, and n is 10 to 300, especially 15 to 100. ).

Therefore, the preferred polysiloxane monomer A'is of formula (A6):

(In the formula, each R ₁ is a methyl group,
X and Y are the same, −CH = CH ₂ , − (CH ₂ ) ₃ −O− (CH ₂ ) − (CHOH) − (CH ₂ ) −OCO-CR = CH ₂ , − (CH ₂ ) _{x '-CH = CH 2 - (} CH 2) x' -CH 2 -OCO-CH = CH 2, -CH 2 -OCO-CH = CH 2, - (CH 2) x '-CH 2 -OCO-CMe _{= CH 2, -CH 2 -OCO-} CMe = CH 2 or - (CH _{2) x} 'represents -SH;
x'is 1 to 5; and n is 15 to 300. ).

Therefore, a more preferred polysiloxane monomer A'is of formula (A7):

(In the formula, each R ₁ is a methyl group,
X and Y are the _{same, -CH = CH 2, - (} CH 2) x '-CH = CH 2, - (CH 2) x' -CH 2 -OCO-CH = CH 2, -CH 2 - _{OCO-CH = CH 2, -} (CH 2) x '-CH 2 -OCO-CMe = CH 2, -CH 2 -OCO-CMe = CH 2, - (CH 2) x' be -SH;
x'is from 1 to 5, especially from 2 to 5, for example 3,; and n is from 15 to 100. ).
As siloxane monomer A'that may be used:
Methacryloxypropyl-terminated PDMS;
(3-Acrylicoxy-2-hydroxypropoxypropyl) terminal PDMS;
Acrylicoxy-terminated ethylene oxide-dimethylsiloxane-ethylene oxide, (ABA type block copolymer);
Vinyl-terminated PDMS can be mentioned.

To produce the binder of the invention, the polysiloxane monomer A'reacts ideally with at least one additional monomer B'or D'. This is the second monomer. Reactions between two monomers generally occur through the reaction of a thiol on one monomer with a vinyl group on the other monomer, or through two thiols that form a disulfide bond. In the second embodiment, the reaction occurs via an amine and a vinyl group.

Thus, in the first embodiment, the reaction can be a thiol-ene reaction or a Michael addition reaction. Those skilled in the art will appreciate that a thiol group can be present on any of the monomers as long as the other monomer contains a reactive group capable of reacting with the thiol group in the polymerization reaction.

It is also essential that the polymer formed contains an ester group in its backbone. These may be derived from monomer B', monomer A', or both.

In the addition copolymerization reaction with the polysiloxane monomer A', it is preferable to use a polyfunctional second monomer. In such an addition polymerization reaction, the two "monomers" preferably react to produce a copolymer having a structure [-ABAB] in which an ester hydrolyzable bond is present. Thus, essentially, the end group of the polysiloxane monomer A'reacts with the end group of the second monomer B'and links via, for example, en or Michael addition chemistry (usually C-NRa-CH ₂ or CS-CH ₂ ) is generated. The resulting polymer hydrolyzes in seawater and thus contains ester groups that ensure that the binders of the invention are self-polishing.

Monomer B'
The second monomer B'has a lower molecular weight than the polysiloxane unit, preferably so that most of the weight of the binder polymer is formed from the polysiloxane residue. Therefore, preferably, the number average Mn of the second monomer B'is less than 2,000, for example less than 1,000, particularly less than 500, for example less than 400.

The Mn of monomer B'is preferably less than 2,000, such as less than 1,000, particularly less than 500, such as less than 300.

Theoretically, the branched monomer B'can be used, and therefore there are more terminal groups than just the W and Z specified in formula (B') above. The use of the branched structure allows the formation of a branched copolymer with the first monomer. However, the use of a bifunctional monomer B'containing essentially two reactive end groups is considered preferred as such monomers allow the formation of essentially linear polymers.

Preferred Monomer B'-Thiol In one embodiment, the polysiloxane monomer A'contains a suitable vinyl end group / SH group and the required ester bond. In such an embodiment, the preferred monomer B'is Formula (BI): HS-Q3-SH (BI).
(In the formula, Q3 is C2-20 alkyl group, C3-20 cycloalkyl group, phenyl group, biphenyl group, terphenyl group, C7-20 alkylaryl group, alkyl-polysiloxane-alkyl, C4-20 alkylcycloalkyl. A group or polyether, wherein the C2-20 alkyl group, C3-20 cycloalkyl group, C7-20 alkylaryl group, or C4-20 alkylcycloalkyl group is one or more, eg, 1 to 4 O. , N, S or P, preferably a hetero atom selected from O;
However, the SH group in the monomer B'reacts with the X and Y groups in the ester containing the monomer A'to form the group C—S—CH ₂ or SS group. ) Is a thiol.

The SH group in the monomer B'is preferably selected to react with the vinyl X and vinyl Y groups in the monomer A'to form the group -C-SCH _2.

Preferably, Q3 represents a C2-16 alkylene group, an alkyl-polysiloxane-alkyl, a phenyl group, a tolyl group, or a biphenyl group.

When Q3 represents a phenyl group, the -SH group is ideally located at 1,3 or 1,4 on the ring. When the Q3 group is a tolyl group, the SH group ideally binds to the phenyl ring rather than the alkyl side chain.

When Q3 represents alkyl-polysiloxane-alkyl, the alkyl group may be a C1-6 alkyl group. The polysiloxane is ideally PDMS and may have n repeating units when n is 1 to 100.

Preferably, the compound of formula (BI) is aliphatic. Preferably, Q3 is a C2-12 alkylene group or a polyether.

If Q3 represents a polyether, it must contain at least two ether bonds. Ideally, these ether bonds are derived from ethylene glycol units. Monomer B'may include 2 to 10 such units. It will be appreciated that there is always an alkyl bond, typically an ethyl or methyl bond, between the O and SH of the polyether, as the SH group cannot be directly attached to the O of the polyether.

It is also possible to use the polyether such that the monomer B'can have Mn in the range of 800 to 10,000, for example 1,000 to 8,000. This can be achieved with PEG groups.

Therefore, Q3 is expressed by the formula −R ⁷ − (OR ⁸ ) _a − (OR ⁸ ) _b −.
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, and a = 0 to 50, b = 0 to 50 and a + b = 1 to 50, respectively.) possible.

Therefore, the preferred monomer B'is HS-Q3-SH (BIV).
(In the formula, Q3 is a C2-16 alkylene group, an alkyl-polysiloxane-alkyl, or a polyether group).

Suitable thiones as monomers BI and BIV are 1,2-ethanedithiol; 1,3-propanedithiol; 1,4-butanedithiol; 1,6-hexanedithiol; 1,8-octanedithiol; 1,9-nonan. Dithiol; 1,11-undecanedithiol; 1,16-hexadecanedithiol; 2,2'-(ethylenedioxy) dietanethiol; tetra (ethylene glycol) dithiol; hexa (ethylene glycol) dithiol; toluene-3,4- Dithiol; 1,3-benzenedithiol; 1,4-benzenedithiol; 1,4-benzenedimethanethiol; biphenyl-4,4'-dithiol p-terphenyl-4,4 "-dithiol; poly (ethylene glycol) Dithiols such as average Mn1,000; poly (ethylene glycol) dithiols such as average Mn 1,500; poly (ethylene glycol) dithiols such as average Mn 3,400; poly (ethylene glycol) dithiols such as average Mn 8,000.

Thus, these thiol monomers B'are combined with monomers A'in which polysiloxane and ester bonds are present and which contain reactive vinyl or SH groups.

Monomer B'is also of formula (BII) or (BIII):

(Wherein, Q1 is a covalent bond, C1-20 alkyl, C3-10 cycloalkyl, C3-10 cycloalkenyl group, C6-10 aryl group, C7-12 arylalkyl group, wherein R ⁷ - (OR ⁸ ) _a - (oR ⁸⁾ polyoxyalkylene chain of ^{_{b -OR 7, -Ph-O-}} C 1-6 alkyl -OPh-, represents a heterocyclyl group, or C4-10 alkylcycloalkyl group;
Here, the C1-20 alkyl group, C3-10 cycloalkyl group, or C3-10 cycloalkenyl group is a hetero selected from 1 or more, for example, 1 to 4 O, N, S or P, preferably O. Arbitrarily containing atoms;
L is a heteroatom selected from 1 or more, eg 1 to 4 O, N, S or P, preferably O or N, or the formula:
− (OR ⁸ ) _a − (OR ⁸ ) _b − OR ^{7 −}
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, and a = 0 to 50, b = 0 to 50 and a + b = 1 to 50, respectively). A C1-20 alkylene group optionally containing a chain;
R is H or Me;
Q2 is a covalent bond, a C1-20 alkyl group, a C3-10 cycloalkyl group, a C2-6 aminoglycol, a C2-6 thioglycol, or a C6-10 aryl group, wherein the C1-20 alkyl group, said. The C3-10 cycloalkyl group, or C3-10 cycloalkenyl group, optionally comprises one or more heteroatoms selected from, for example, 1 to 4 O, N, S, or P, preferably O. ) And;
W and _{Z, -SH, - (CR "2} ) x 'SH, CH 2 = CR-, CH 2 = CR- (CR" 2) x' -, - C≡CH, -NHCH 2 -CR = CH ₂ , NHCH _2- CR≡CH-NHRa, -NHRa, or W and Z are = CH ₂ (hence the C atom to which the W / Z forming the double bond is attached); W and Z _{is, -SH, - (CR "2} ) x 'SH, CH 2 = CR-, CH 2 = CR- (CR" 2) x' -, - C≡CH, -NHCH 2 -CR = CH 2, NHCH ₂ −CR≡CH-NHRa, −NHRa, or W and Z are = CH ₂ (hence the C atom to which the W / Z forming the double bond is attached);
Ra is an H or C1-6 alkyl group, wherein the alkyl group optionally comprises one or more, eg, 1 to 4 O, N, S or P, preferably a heteroatom selected from O. ;
"R" is independently a C _1-6 alkyl group or H, especially H;
x'is from 1 to 10, for example 1 to 5, especially 2 to 5, especially 3 to 5;
However, the W and Z groups in the monomer B'react with the X and Y groups in the monomer A'to form the group C—S—CH ₂ or SS group. ).

When the monomer B'is represented by the formula BII, it is preferably terminated within a vinyl or alkynyl group. In this scenario, the polysiloxane contains the required thiol groups.
Q1 is preferably a C1-20 alkyl group, a C3-10 cycloalkyl group, a C3-10 cycloalkenyl group, a C6-10 aryl group, a C7-12 arylalkyl group, or a C4-10 alkylcycloalkyl group.

More preferably, Q1 is a C2-10 alkyl group, a C3-8 cycloalkyl group, a C3-8 cycloalkenyl group, a C6-10 aryl group, a C7-12 arylalkyl group, or a C4-10 alkylcycloalkyl group. ..

Q2 is preferably a covalent bond, a C1-20 alkyl group, a C3-10 cycloalkyl group, a C2-6 aminoglycol, a C2-6 thioglycol, or a C6-10 aryl group.

Q2 is more preferably a covalent bond, a C1-10 alkyl group, a C3-8 cycloalkyl group, a C2-6 aminoglycol, a C2-6 thioglycol, or a C6-10 aryl group.

L is preferably a C1-10 alkylene group, such as a C1-5 alkylene group or formula:
− (OR ⁸ ) _a OR ⁷ −
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, and a = 0 to 50, respectively).

W and Z are preferably -SH, -CH _2- SH, CH ₂ = CR-, CH ₂ = CR-CH _2- , or W and Z are = CH ₂ . W and Z are more preferably -SH, -CH _2- SH, CH ₂ = CR- or CH ₂ = CR-CH _2- . W and Z are more preferably CH ₂ = CR- or CH ₂ = CR-CH _2- .

In one embodiment, L comprises N heteroatoms in its skeleton. Therefore, L _{is, - (CH 2) x '} -NH- (CH 2) x' ( wherein, x 'is independently a 1 to 5.) Is. In one embodiment, the L group is a polyoxyalkylene chain, and W and Z are -NHCH _2- CR = CH ₂ .

Therefore, the preferred monomer B'is the formula BV or BVI.

(In the formula, Q1 is a C2-10 alkyl group, a C3-8 cycloalkyl group, a C3-8 cycloalkenyl group, a C6-10 aryl group, a C7-12 arylalkyl group, or a C4-10 alkylcycloalkyl group. ;
Q2 is a covalent bond, a C1-10 alkyl group, a C3-8 cycloalkyl group, a C2-6 aminoglycol, a C2-6 thioglycol, or a C6-10 aryl group;
R is Me or H;
L is preferably a C1-10 alkylene group, such as a C1-5 alkylene group or formula:
− (OR ⁸ ) _a OR ⁷ −
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, and a = 0 to 50, respectively).
W and Z are -SH, -CH _2- SH, CH ₂ = CR-, CH ₂ = CR-CH _2- , or W and Z are = CH ₂ . ).

Therefore, the preferred monomer B'is the formula BX.

(In the formula, Q1 is a C2-10 alkyl group, a C3-8 cycloalkyl group, a C3-8 cycloalkenyl group, a C6-10 aryl group, a C7-12 arylalkyl group, or a C4-10 alkylcycloalkyl group. ;
R is Me or H;
L is preferably a C1-10 alkylene group, such as a C1-5 alkylene group or formula:
− (OR ⁸ ) _a OR ⁷ −
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, and a = 0 to 50, respectively).
W and Z are -SH, -CH _2- SH, CH ₂ = CR-, CH ₂ = CR-CH _2- , or W and Z are = CH ₂ . ).

It is particularly preferred to combine the monomers A5 to A7 with BIV to BVI or BIX. For example, a suitable monomer (BII) can be described in the following scheme:

As shown in, it can be synthesized from cyclic anhydride and vinyl alcohol or propargyl alcohol.

In these compounds, R ₁₀ represents a ring-forming group. Preferably, R ₁₀ is with a C1-8 alkyl group or a carbon atom to which it is bonded to form a C3-10 ring fused to a C6-10 aromatic ring or an anhydride ring (thus giving rise to a bicyclic system). It is R _{10 together.} R ₁₀ is preferably combined with a C1-4 alkyl group or a carbon atom to which it is bonded to form a 6-membered aliphatic ring (eg, a C6 alkenyl ring) from a 6-membered aromatic ring or a 5-membered aliphatic ring. It is now R ₁₀ .

In the vinyl alcohol component, R is H or Me. R ₁₁ is a C1-6 alkyl group. R ₁₁ may be a linear or branched C1-6 alkyl group. Other possible vinyl alcohols are listed below.

The reaction is an allyl reaction product:

Also included is an ether comprising (preferably 1 to 10, for example 1 to 3).

Suitable reactants for these processes are: succinic anhydride, methylsuccinic anhydride, glutaric anhydride, phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, homophthalic anhydride, 3, 3-Dimethylglutaric anhydride.

Suitable vinyl alcohols include allyl alcohol, 2-methyl-2-propen-1-ol; 3-butene-2-ol, diethylene glycol monoallyl ether.

Those skilled in the art know other pathways for obtaining monomeric B'type monomers. For example, amino-containing monomers have the following scheme:

(In the formula, Q1, R and R11 are as defined above).

Allylamine or propargylamine can also be pre-reacted with ethylene oxide units to make alkene / alkyne functional polyethers.

In the second embodiment, the monomer B'is a dicarboxylic acid or a derivative thereof:

(In the formula, Q1 is defined above as C1-20 alkyl group, C3-10 cycloalkyl group, C3-10 cycloalkenyl group, C6-10 aryl group, C7-12 arylalkyl group or C4-10 alkylcycloalkyl group. It can be formed from). Those skilled in the art will appreciate that carboxylic acids can be converted to their corresponding esters or acid halides to aid in this reaction, if desired.

In one embodiment, the following scheme:

(Here, R ₁₃ is a polyether such as a C2-20 alkyl group, a C2-20 ether, or a polyethylene glycol-alkyl group.) From the reaction of a mercapto alcohol with a diacid or a derivative thereof. Monomer B'can be prepared.

R ₁₃ is preferably of the formula −R7− (OR8) a− (OR8) b−.
(Here, R7 and R8 are independently C2-6 alkylene groups, respectively, and a = 0 to 50, b = 0 to 50, and a + b = 1 to 50). When expressed, Q1 is as defined above.

Suitable dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,3-bis (4-carboxyphenoxy) propane, pimelic acid, benzene-1,4-dicarboxylic acid, 1,4. Cyclohexanedicarboxylic acid, poly (ethylene glycol) bis (carboxymethyl) ether, average Mn250, poly (ethylene glycol) bis (carboxymethyl) ether, average Mn600 can be mentioned.

Suitable mercapto alcohols include mercapto alcohol, 2-mercaptoethanol, 3-mercapto-1-propanol, 4-mercapto-1-butanol, 6-mercapto-1-hexanol, 8-mercapto-1-octanol, 11-mercapto. -1-Undecanol and 2- {2- [2- (2-mercaptoethoxy) ethoxy] ethoxy} ethanol can be mentioned.

In a particularly preferred embodiment, the polymer is a reaction product of a (meth) acryloxyalkyl-terminated polysiloxane monomer with a bisthiol monomer such as a thiol-terminated polyester monomer.

In a particularly preferred embodiment, the polymer is a reaction product of a thiol-terminated polysiloxane monomer and a vinyl-terminated polyester monomer.

In a particularly preferred embodiment, the polymer is a reaction product of a vinyl-terminated polysiloxane monomer and a thiol-terminated polyester monomer.

In one embodiment, the polymer is a reaction product of a thiol-terminated polysiloxane monomer and a thiol-terminated polyester polyol monomer.

Amine Aspects In a second aspect, the invention relates to a binder in which the polymer is obtained from the reaction of an amine monomer with a vinyl or alkynyl-terminated monomer such as a (meth) acrylate-terminated polysiloxane and an amine monomer.

In a particularly preferred embodiment, the polymer is a reaction product of a (meth) acryloxyalkyl-terminated polysiloxane monomer with an amine-terminated monomer such as an amine-terminated polyester monomer.

In another preferred embodiment, the polymer is a reaction product of an amine-functionalized polysiloxane monomer and a vinyl-terminated polyester monomer.

In a preferred embodiment, the polymer is a reaction product of a (meth) acryloxialkyl-terminated polysiloxane monomer with an amine-terminated polysiloxane monomer.

As long as the polysiloxane monomer is a (meth) acryloxialkyl-terminated polysiloxane monomer, such a monomer is as detailed above as monomer A'. Specific particularly preferred (meth) acryloxialkyl-terminated polysiloxane monomers are further described below. In a further embodiment, such a monomer can be an amine terminal. These are referred to herein as monomer C'.

Seen from another aspect, the present invention describes the general formulas (C1) to (C2):

(In the formula, each R ₁ is the same or different, unsubstituted or substituted C _1-20 alkyl group, C _2-20 alkenyl group, C _3-20 cycloalkyl group, C _6-20 aryl group, C _7-20. Represents an arylalkyl group, or polyoxyalkylene chain;
X and Y may be different even in the _{same, - (CR "2) x} '-NRaH, - (CR" 2) x' -NH- (CR "2) -NRaH, - (CR" _{2) x} ', -O- (C1-6 _{alkyl) x' -NRaH, - (CR} "2) x '-O- (CR" 2) x' -NRaH or -CR _"2 -Ar-CR" ₂ -NH ₂ where the alkyl group can be disrupted by a heteroatom. ) Represents;
"R" is independently a C _1-6 alkyl group or H, especially H;
Ra is an H or C _1-6 alkyl group;
x'is 1 to 10, for example 1 to 5, especially 2 to 5, especially 3 to 5, and n is 1 to 500, more preferably 10 to 300, especially 15 to 100;
Alternatively, n'+ m is 1 to 500 in total, more preferably 10 to 300, and particularly 15 to 100. ), A binder for a marine coating composition containing a reaction product of at least one polysiloxane monomer C'is provided.

In the preferred monomer C', R ₁ is a methyl group. In this aspect, the use of PDMS is also preferred. Preferably, X and Y are the same.

'In, X and Y are, - (CH _{2) x'} Preferred monomers _{C -NRaH, - (CH 2)} x '-NH- (CH 2) -NRaH, - (CH 2) x' -O- (CH _{2) x '-NRaH, - (} CH 2) x' - and (O-C _{1-6 alkyl) x '-NRaH, -CH 2 -Ar} -CH 2 -NH 2 represents. More preferably, X and Y are − (CH ₂ ) _{x ′} −NRaH.

Ra is preferably H. Accordingly, monomers C 'and most preferably X and Y groups in _{the, - (CH 2) x'} -NH 2, - (CH 2) x '-NH- (CH 2) x' -NH 2, - (CH _{2) x '-O- (CH 2} ) x' -NH 2, - (CH 2) x '-O- (CH 2 CH (CH 3)) is x'-NH _2.

Preferred amine monomer C's include alpha-amino and omega-amino (primary and secondary) functional siloxanes having a total chain length of 10 to 100.

The preferred monomer C'is

(Wherein, X and Y are the _{same, - (CH 2) x '} -NRaH, - (CH 2) x' -NH- (CH 2) -NRaH, - (CH 2) x '-O- _{(CH 2) x '-NRaH,} - (CH 2) x' -O- (C 2-6 alkyl) _x '-NRaH, represents a _{-CH 2 -Ar-CH 2 -NH 2} , in particular X and Y , - (CH _{2) x} 'is -NRaH,
x'is from 1 to 10, for example 1 to 5, especially 2 to 5, especially 3 to 5;
Ra is an H or C1-6 alkyl group; and n is 1 to 500, more preferably 10 to 300, especially 15 to 100; or n'+ m is 1 to 500 in addition, more preferably. 10 to 300, especially 15 to 100. ).

The preferred monomer C'is

(Wherein, X and Y groups are the _{same, - (CH 2) x '} -NH 2, - (CH 2) x' -NH- (CH 2) x '-NH 2, - (CH 2 _{) x '-O- (CH 2)} x' -NH 2, - (CH 2) x '-O- (CH 2 CH (CH 3)) x' represents -NH _2;
x'is 1 to 5; and n is 1 to 500, more preferably 10 to 300, especially 15 to 100. ).

In a preferred embodiment, when the second monomer is an amine D', the monomer A'contains a (meth) acryloxyalkyl group. The preferred monomer A'is the general formula (A8):

(In the formula, each R ₁ is the same or different, unsubstituted or substituted C _1-20 alkyl group, C _2-20 alkenyl group, C _3-20 cycloalkyl group, C _6-20 aryl group, C _7-20. Represents an arylalkyl group, or polyoxyalkylene chain;
X and Y may be different even in the _{same, - (CH 2) x '} -CH 2 -OCO-CR = CH 2, or an _{-CH 2 -OCO-CR = CH 2} ;
x'is from 1 to 10, for example 1 to 5, especially 2 to 5, especially 3 to 5;
Each R is independently H or Me; and n is 1 to 500, more preferably 10 to 300, especially 15 to 100. ).

More preferably, monomer A'

(Wherein, X and Y may be different even in the same, - (CH _{2) x} 'represents the -CH ₂ -OCO-CR = CH ₂ or -CH ₂ -OCO-CR = CH ₂ ;
x'is from 1 to 10, for example 1 to 5, especially 2 to 5, especially 3 to 5;
Each R is independently H or Me; and n is 1 to 500, more preferably 10 to 300, especially 15 to 100. ).

Preferred monomers C'are amine-terminated PDMS, such as Tegomer® A-Si2122, Tegomer® A-Si2322.

When the polysiloxane monomer A'is vinyl-terminated with a (meth) acryloxyalkyl group or the like, the second monomer needs to be an amine-terminated monomer in order to form an amine bond.

In one embodiment, the monomer is of formula HRaN-Q5-NHRa (D1).
(In the formula, Q5 is a C2-20 alkyl group, a C2-20 alkenyl group, a C3-20 cycloalkyl group, a phenyl group, a biphenyl group, Ph-O-Ph, a terphenyl group, a C7-20 alkylaryl group, and an alkyl. -Polysiloxane-alkyl, C4-20 alkylcycloalkyl group, heterocyclyl group or polyether, wherein the C2-20 alkyl group, C3-20 cycloalkyl group, C7-20 alkylaryl group, or C4-20. Alkylcycloalkyl groups optionally contain one or more heteroatoms selected from, for example, 1 to 4 O, N, S or P, preferably O;
Ra is an H or C1-6 alkyl group;
However, the amine group in the monomer D'reacts with the X and Y groups in the ester containing the monomer A'. ) Monomer D'. Alternatively, when monomeric C'is used, the formula (BXX) or (BXI) is preferred.

(Wherein, Q1 is a covalent bond, C1-20 alkyl, C3-10 cycloalkyl, C3-10 cycloalkenyl group, C6-10 aryl group, C7-12 arylalkyl group, wherein R ⁷ - (OR ⁸ ) _{Represents a-} (OR ⁸ ) _b- OR ⁷ polyoxyalkylene chain, -Ph- _{OC 1-6} alkyl-OPh-, heterocyclyl group or C4-10 alkylcycloalkyl group;
Here, the C1-20 alkyl group, C3-10 cycloalkyl group, or C3-10 cycloalkenyl group is a hetero selected from 1 or more, for example, 1 to 4 O, N, S or P, preferably O. Arbitrarily containing atoms;
L is 1 or more, for example from 1 4 O, N, S or P, the heteroatom preferably selected from O or N, or wherein _{^{:-( OR 8,) a - (}} OR 8) b -OR 7 -
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, and a = 0 to 50, b = 0 to 50, and a + b = 1 to 50, respectively). A C1-20 alkylene group optionally containing an oxyalkylene chain;
R is H or Me;
Q2 is a covalent bond, a C1-20 alkyl group, a C3-10 cycloalkyl group, a C2-6 aminoglycol, a C2-6 thioglycol, or a C6-10 aryl group, wherein the C1-20 alkyl group. The C3-10 cycloalkyl group, C3-10 cycloalkenyl group optionally comprises one or more heteroatoms selected from, for example, 1 to 4 O, N, S, or P, preferably O;
W and Z _{are, CH 2 = CR-, CH 2} = CR-CH 2 -, - NHCH 2 -CR = CH 2, a -C≡CH, or W and Z, = CH ₂ (therefore, W / It forms a double bond with the C atom to which Z is bonded);
Ra is an H or C1-6 alkyl group;
However, the W and Z groups in the monomer B'react with the amino X and Y groups in the monomer C'to form the C-NRa-CH ₂ -group. ) In combination with monomer D'.

Alternatively, when monomeric C'is used, the formula (BXXI) is preferred.

(In the formula, Q1 is a C2-10 alkyl group, a C3-8 cycloalkyl group, a C3-8 cycloalkenyl group, a C6-10 aryl group, a C7-12 arylalkyl group, or a C4-10 alkylcycloalkyl group. ;
L is preferably a C1-10 alkylene group, such as a C1-5 alkylene group or formula:
− (OR ⁸ ) _a OR ⁷ −
(Here, R ⁷ and R ⁸ are independently C _2-4 alkylene groups, a = 0 to 50); and R is H or Me. ;
W and Z _{are, CH 2 = CR-, CH 2} = CR-CH 2 -, - NHCH 2 -CR = CH 2, a -C≡CH, or W and Z, = CH ₂ (therefore, W / It forms a double bond with the C atom to which Z is bonded);
However, the W and Z groups in the monomer B'react with the amino X and Y groups in the monomer C'to form the C-NRa-CH ₂ -group. ) Combined with monomer D'.
Particularly preferably, D'is
HRaN-Q5-NHRa (DII)
(In the formula, Q5 is a C2-10 alkyl group, C _1-6 alkyl-polysiloxane-C _1-6 alkyl;
Ra is an H or C1-6 alkyl group and the polysiloxane component is ideally PDMS, which ideally reacts with the monomers A8 or A9. ).
Possible amine reagents are: ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, m-xylylene diamine, 2,2'-biphenyldiamine, 4,4'-oxydianiline, N, N'-diethyl-2. -Butene-1,4-diamine, 1,2,4-thiasiazol-3,5-diamine, poly (ethylene glycol) diamine, Mn2000; poly (ethylene glycol) diamine, Mn3000, poly (ethylene glycol) diamine, Mn6, 000; poly (ethylene glycol) diamine, Mn 10,000.

When combined with the vinyl-terminated monomer A', the monomer B'is of formula (BVII).

(In the formula, Q1 is a C1-20 alkyl group, a C3-10 cycloalkyl group, a C3-10 cycloalkenyl group, a C6-10 aryl group, a C7-12 arylalkyl group, and a formula R ⁷ − (OR ⁸ ) _a −. (OR ⁸ ) represents a polyoxyalkylene chain of _b- OR ⁷ _{, -Ph-OC 1-6} alkyl-OPh-, a heterocyclyl group or a C4-10 alkylcycloalkyl group; where the C1-20 alkyl group is described. , C3-10 cycloalkyl group, or C3-10 cycloalkenyl group optionally comprises one or more heteroatoms selected from, for example, 1 to 4 O, N, S or P, preferably O;
L is a C1-20 alkyl group, formula:
− (OR ⁸ ) _a − (OR ⁸ ) _b − OR ^{7 −}
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, a = 0 to 50, b = 0 to 50 and a + b = 1 to 50; and Ra is H or It is a polyoxyalkylene chain of C1-6 alkyl group). ).

Therefore, the preferred monomer B'is of formula BVIII.

(In the formula, Q1 is a C2-10 alkyl group, a C3-8 cycloalkyl group, a C3-8 cycloalkenyl group, a C6-10 aryl group, a C7-12 arylalkyl group, or a C4-10 alkylcycloalkyl group. ;
L is preferably a C1-10 alkylene group, such as a C1-5 alkylene group, or formula:
− (OR ⁸ ) _a OR ⁷ −
(Here, R ⁷ and R ⁸ are independently C _2-4 alkylene groups, a = 0 to 50; and Ra is an H or C 1-6 alkyl group.) Polyoxy It is an alkylene chain. ).

Suitable reagents of formula BVII / BVIII can be prepared in the same manner as the thiol reactants described above. For example, cyclic anhydrides (eg, as described above) are aminoalcohols:

(Here, R ₁₀ and R ₁₃ are as defined above.).

Suitable amino alcohols are 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 3-methylamino-1-propanol, N- (2-hydroxyethyl) aniline, 2-benzylaminoethanol.

Suitable reagents include succinic anhydride, methylsuccinic anhydride, glutaric anhydride, phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, homophthalic anhydride, and 3,3-dimethylglutaric anhydride. , Dimethyl succinate, dimethyl adipate, dimethyl succinate, dimethyl terephthalate, dimethyl cyclohexane-1,4-dicarboxylate.

Introduction of Polyethers In a preferred embodiment, the monomers are designed so that one of them introduces a polyether group into the backbone of the molecule, such as a group of the type polyethylene glycol or polypropylene glycol. Incorporated poly (oxyalkylene) such as PEG, PPG can have Mn of 50 to 5,000, such as 50 to 2,000, more preferably less than 1,000. Preferably, PEG having 1 to 100, more preferably 1 to 50, especially 2 to 30, repeating units is used.

The presence of the polyether will help regulate the water absorption of the polymer film formed with the binder. Then, the hydrogel-like property of PEG, which causes inactivity to protein adsorption, can be added.

Therefore, in the preferred option, the monomer B'contains ethylene glycol or propylene glycol repeating units.

Therefore, monomer B'can contain residues of PEG or PPG molecules.

The above description allows one of ordinary skill in the art to design various binders that meet the requirements of the functional definition of the claims.

Binder It will be appreciated that it is difficult to devise a general formula that covers all possible choices.

The binder of the present invention preferably has a number average molecular weight Mn of 2,000 to 100,000, for example 5,000 to 80,000, particularly 10,000 to 50,000.

The binder of the present invention has a very low glass transition temperature, such as 0 ° C. or lower, preferably −50 ° C. or lower, particularly −100 ° C. or lower.

The endcapping polymer may have terminal groups represented by F and G. The groups F and G are as defined above for X and Y (or W and Z), or the groups F and G can be derived by endcapping or end modification after polymerization of the copolymer. End capping / end modification means post-polymerization functionalization of end groups that are naturally formed during copolymerization to include curable end groups or end groups capable of reacting with crosslinkers. Crosslinking can also be facilitated through functionalization _{of the R 1} side group, such as by pendant functionalization after polymerization or functionalization of organic B monomer residues. F and G may be the same or different, typically the same as one of the slightly excess monomers used in the polymerization. Preferably, F and G are alkoxy groups such as trialkoxysilane groups such as triethoxysilane groups or trimethoxysilane groups.

Ideally, the groups F and G are cross-linking groups, i.e. they are curable with or without the addition of cross-linking agents. The options for cross-linking the binder polymer are described in detail below.

It will also be appreciated that the binder can include different polysiloxane monomers A'and second and third monomers B'. Therefore, the possibility of forming a terpolymer or the like is also within the scope of the present invention.

Copolymer binders are obtained by mixing all starting materials prior to polymerization or by adding one of the monomers during the reaction. It will be appreciated that those skilled in the art know how to carry out the polymerization depending on the monomer used. The binder formed is typically an alternating ABABAB polymer of the units used, unless the target polymer is a disulfide. It will be appreciated that the polysiloxane unit should preferably not polymerize with itself and the second monomer should preferably not polymerize with itself.

If the target polymer is a disulfide (and therefore both monomers have terminal SH groups), the monomers can react with themselves under polymerization conditions. The resulting polymer is a monomer-based random copolymer.

The polymer is preferably not a block copolymer. With two second monomers Ba and Bb, the pattern is preferably AXAXAX, where X is randomly selected from Ba or Bb. The amount of Ba and Bb present will depend on the stoichiometry of the polymerization.

Polymerization conditions can vary widely, but typically temperatures from 20 ° C to 250 ° C, such as 40 ° C to 22 ° C, are used. If the polymerization in question is a condensation polymerization, a condensate (usually water or alcohol) is formed. This is preferably removed by distillation as the polymerization continues. This can be achieved under reduced pressure. The polymerization is preferably carried out under an inert atmosphere, such as a nitrogen atmosphere or especially nitrogen stripping conditions. If the polymerization in question is an addition polymerization, one supply of monomers is preferred for controlling exothermic reactions, or especially for controlling the molecular design of the end groups.

The binder of the present invention preferably has a number average molecular weight (Mn) greater than at least 5,000 g / mol, preferably at least 10,000 g / mol, more preferably at least 15,000 g / mol, and particularly 20,000 g / mol. Have. In a particularly preferred embodiment, a value exceeding 10,000 g / mol is preferable. The number average molecular weight is preferably up to 100,000 g / mol, for example up to 80,000 g / mol.

However, there is a trade-off because if Mn is made too large, the viscosity will increase and more solvent will be required to ensure that the coating composition can be applied. More solvents increase the unwanted volatile organic content.

Of course, it will be appreciated that the binder as a whole can be made from a mixture of two or more binders with different Mn and / or different hydrolyzing properties / rates, i.e. different hydrolyzing groups and content of hydrolyzing groups. By changing the properties of the binder component, the rate of hydrolysis can be changed.

Preferably, the binder forms at least 30% by weight, for example at least 40% by weight, for example at least 50% by weight of the coating composition. The binder can be formed up to 80% by weight or less, for example 70% by weight or less, for example 60% by weight or less of the coating composition.

Crosslinkers and hardeners In some embodiments of the present invention, it is preferable to crosslink the binder polymer in use. The binder polymer of the present invention may have curable end groups due to the nature of the groups used to form the binder polymer or endcapping. Preferably, the end groups of the polymer can be endcapped with reactive groups to cause a cross-linking reaction. A particularly interesting endcapping group is trialkoxysilane.

The binder of the present invention can be crosslinked in the absence or presence of a curing agent.

For example, examples of curing agents well known in the art include monomeric isocyanates, polymer isocyanates and isocyanate prepolymers. Polyisocyanates are preferred over monomeric isocyanates due to their low toxicity. For example, polyisocyanates can be based on the chemistry of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). For example, they are offered under the trade name Desmodur by Bayer Materials Science and under the trade name Tolonate by Vencorex. Examples of polyisocyanates are Desmodur N3400, Desmodur N3300, Desmodur N3600 Desmodur N75, Desmodur XP2580, Desmodur Z4470, Desmodur XP2565 and Desmodur VL from Desmodur XP2565 and Desmodur VL.

Polyisocyanates can be produced with different NCO-functionality. NCO-functionality is the amount of NCO-groups per polyisocyanate molecule or isocyanate prepolymer molecule. Polyisocyanate curing agents with different NCO-functionality can be used.

The curing agent is preferably 0.8 to 1.5 equivalents (equivalent) of NCO groups relative to the amount of hydroxyl groups, preferably 0.9 to 1.4 equivalents, more preferably 0.95 to 1.3. It is present in equivalents, and even more preferably 1 to 1.2 equivalents.

The functionality of the end groups of the binder will depend on the starting monomer. The terminal group can be easily modified to other functional groups suitable for a wide range of curing reactions. Examples of other curable end groups include epoxy groups.

For example, an ethylenically unsaturated group such as a (meth) acrylate group causes the thiol group in the binder to react with an ethylenically unsaturated carboxylic acid such as acrylic acid or methacrylic acid, or a slight excess of (meth) acrylate monomer. It can be introduced by using it.

Therefore, preferably, the binder contains essentially curable end groups or is modified to contain curable end groups. Compounds modified to include curable end groups may be particularly referred to as end group modified binders (or end cap modified binders).

Another end group modifier is one that includes an alkoxysilane such as a monoalkoxysilane, dialkoxysilane or trialkoxysilane. Current commercial fouling release coatings are generally cured by a condensation curing mechanism that involves the hydrolysis of ethoxysilane (methoxysilane) compounds. This has the advantage of minimizing the amount of polar entities introduced (which increases the polar interaction with the type of fouling) compared to, for example, isocyanate-based cross-linking. In order to promote a similar condensation curing mechanism for the binder of the present invention, an endcapping reaction of terminal functional groups can be carried out.

For example, an alkoxysilane such as vinyltrimethoxysilane can be used to alter the terminal SH group.

Thus, in a further embodiment, the binder is the group −SiR ” _d (OR') _3-d (where d = 0 to 2, R” and R ′ are independently _{selected from the C 1-6} alkyl groups. It is end capped with a compound containing). Examples are trimethoxysilyl, triethoxysilyl, methyldiethoxysilyl, methyldimethoxysilyl, dimethylmethoxysilyl and dimethylethoxysilyl. The compound as a whole contains this siloxy group and additional functional groups capable of reacting with the terminal groups on the formed copolymer binder. The endcapping unit is ideally a low molecular weight compound with Mn up to 400.

Examples of compounds used are vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane. , And allyltrimethoxysilane. In the presence of water, the siloxy-terminated groups present at the end of the binder begin to crosslink. In some cases, the end group may be monoethoxysilane (monomethoxysilane), in which case an alkoxysilane such as tetraethoxysilane or a condensate thereof (eg, WACKER®). ) TES40WN)) may be used to cure the coating.

The cross-linking agent preferably constitutes 0% to 10% by dry weight of the coating composition, and for example, the general formula (2): R _d- Si-V _4-d (2) shown below.
(In the formula, each R independently represents an unsubstituted or substituted monovalent hydrocarbon group of carbon atoms 1 to 6, each V independently represents a hydrolyzable group, and d is 0. , For example, representing an integer from 0 to 1), a partially hydrolyzed condensate thereof, or a mixture of the two.

Mixing of the binder polymer with the curing agent can be performed shortly before applying the coating to the object, eg within 1 hour of coating, or the binder can be provided in a curable form, but to prevent premature curing. Can be kept dry. In some embodiments, the curing agent / endcapping agent is provided separately for the rest of the coating composition to prevent curing before the coating is applied to the object. When the terminal is monoethoxysilane (monomethoxysilane), a monoethoxysilane (monomethoxysilane) cross-linking agent, for example TES 40 WN, can be used in combination with a binder. Therefore, the coating composition of the present invention can be provided as a multi-pack (preferably 2-pack) formulation.

Therefore, in another aspect, the invention provides a kit comprising (I) the binder polymer described herein and (II) curing. Preferably, instructions will be provided to mix the ingredients shortly before application. A catalyst may be provided for one or the other components to facilitate the cross-linking process.

Coating Composition The coating composition of the present invention comprises a binder or a mixture of binders. The composition may also contain other conventional components of the fouling release composition.

Polysiloxane-based binder systems typically make up 20% to 90% by dry weight of the coating composition, at least 40% by dry weight, particularly 50% to 90% by dry weight.

The binder of the present invention decomposes in seawater. It will be appreciated that the degradation reaction that the binder undergoes is a hydrolysis reaction that occurs in the polymer backbone, i.e., that hydrolyzable bonds are present in the polymer backbone.

In addition to the binder, the coating compositions of the present invention may contain other components such as additive oils, catalysts, biocides, enzymes and co-binders. Other conventional ingredients include solvents, additives, pigments and fillers.

The additive oil coating composition may include, for example, the well-known hydrophilic modified additive oil described in WO 2011/068656. The composition may further comprise a hydrophilic modified polysiloxane oil, i.e., a component that does not form a covalent bond with the ester siloxane-based binder matrix. Hydrophilic modified polysiloxane oils are widely used as surfactants and emulsifiers because they contain both hydrophilic and lipophilic groups in the same molecule. In contrast to the ester siloxane component described above, the hydrophilic modified polysiloxane oil is selected to be free of groups capable of reacting with the binder (or binder component) or cross-linking agent (if present), and thus the hydrophilic modified polysiloxane. The oil is intended to be non-reactive, especially with respect to the binder component. In particular, hydrophilic modified polysiloxane oils include silicon-reactive groups such as Si-OH groups and Si-OR groups (eg alkoxy, oxime, acetoxy) to avoid reaction with the components of the ester silane-based binder system. ) And other hydrolyzable groups.

Non-reactive hydrophilic modified polysiloxane oils are usually modified by the addition of non-ionic oligomeric or polymer groups that can be polar and / or hydrogen bondable and are polar solvents, especially water, or other polar oligomeric groups. Or enhance the interaction with polymer groups. Examples of these groups include amides (eg poly (vinylpyrrolidone), poly [N- (2-hydroxypropyl) methacrylicamide]), poly (N, N-dimethacrylamide), acids (eg poly (acrylic acid). ), Alcohol (eg poly (glycerol), poly HEMA, polysaccharides, poly (vinyl alcohol)), ketones (polyketone), aldehydes (eg (poly (aldehyde gluronate), amines (eg polyvinylamine), esters (eg For example, polycaprolactone, polyvinyl acetate)), ethers (eg, polyoxyalkylenes such as poly (ethylene glycol), poly (propylene glycol)), imides (eg, poly (2-methyl-2-oxazoline)), etc. Examples include copolymers.
Preferably, hydrophilicity is obtained by modification with a polyoxyalkylene group. In a preferred embodiment, the hydrophilic modified polysiloxane oil (if present) is in the range of 100 g / mol to 100,000 g / mol, eg, 250 to 75,000 g / mol, particularly 500 to 50,000 g / mol. It has a range of number average molecular weight (Mn).

One or more hydrophilic modified polysiloxane oils are included in the coating composition in an amount of 0.01% to 30%, eg 0.05% to 10% by dry weight. In certain embodiments, the one or more hydrophilic modified polysiloxane oils are 0.05% to 7% by dry weight of the coating composition, eg 0.1% to 5% by dry weight, especially 0. It constitutes 5% to 3%.

Other interesting additive oils are described in WO 2008132196. Suitable non-reactive fluids are silicone oils such as methylphenyl silicone oil, polydimethylsiloxane, carboxyl-functional organosiloxanes disclosed in WO 2008/132195, petroleum, polyolefin oils, polycyclic aromatic oils. , Fluororesin such as polytetrafluoroethylene or alkyl fluorinated or alkoxy-containing polymer, or lanolin and lanolin derivatives and other sterols and / or sterol derivatives disclosed in PCT application PCT / European Patent Application Publication No. 2012/0659220. Or a combination thereof. A preferred non-reactive fluid is methylphenyl silicone oil. Also of interest are the fluorinated amphipathic polymers / oligomers described in WO 2014131695. The proportion of unreacted fluid is preferably 5% to 25% by weight, more preferably 5% to 10% by weight, based on the amount of solids in the coating composition.

Biocide / Marine Antifouling Agent In one embodiment, the biocide can be used in the binder of the present invention. Suitable biocides are well known and can be found in WO 2013/000479.

In this context, the term "biocide" is an active substance intended to destroy, deter, detoxify, prevent or control harmful marine organisms by chemical or biological means. Is intended to mean. Examples of killing agents are metallo-dithiocarbamic acids such as zinc bis (dimethyldithiocarbamic acid), zinc ethylene-bis (dimethyldithiocarbamic acid), manganese ethylene-bis (dimethyldithiocarbamic acid), and complexes between them; bis ( 1-Hydroxy-2 (1H) -pyridine-thionate 0, S) -copper; copper acrylate; bis (1-hydroxy-2 (1H) -pyridinethionate 0, S) -zinc; phenyl (bispyridyl) -2 Bismus chloride; metal killing agents such as copper metal alloys such as copper (I) oxide, cuprous oxide, metallic copper, copper nickel alloys; cuprous thiocyanate, basic copper carbonate, copper hydroxide, barium metaborate, Metal salts such as copper sulfide; 3a, 4,7,7a-tetrahydro-2-((trichloromethyl) -thio) -1H-isoindole-1,3 (2H) -dione, pyridine-triphenylborane, 1- (2,4,6-trichloro-phenyl) -1H-pyrrole-2,5-dione, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, 2-methylthio-4-tert- Heterocyclic nitrogen compounds such as butylamino-6-cyclopropylamine-s-triazine, and quinoline derivatives; 2- (4-thiazolyl) benzimidazole, 4,5-dichloro-2-n-octyl-4-isothiazolin-3 -On, 4,5-dichloro-2-octyl-3 (2H) -isothiazolin (Sea-Nine <(registered trademark)> -211N), 1,2-benzoisothiazolin-3-one, and 2- (thiosia) Heterocyclic sulfur compounds such as natemethylthio) -benzothiazole; N- (1,3-bis (hydroxymethyl) -2,5-dioxo-4-imidazolidinyl) -N, N'-bis (hydroxymethyl) urea, N -(3,4-Dichlorophenyl) -N, urea derivatives such as N-dimethylurea, Ν, Ν-dimethylchlorophenylurea; carboxylic acid amides or imides; 2,4,6-trichlorophenylmaleimide, 1.1-dichloro -N-((dimethylamino) sulfonyl) -1-fluoro-N- (4-methylphenyl) -methanesulfenamide, 2.2-dibromo-3-nitrilopropionamide, N- (fluorodichloromethylthio) -phthalimide , N, N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio) -sulfamide, and sulfonic acids and sulfene such as N-methylolformamide. Acids; salts or esters of 2-((3-iodo-2-propynyl) oxy) -ethanolphenylcarbamate and carboxylic acids such as N, N-didesyl-N-methyl-poly (oxyethyl) ammonium propionate; dehydroabi Amines such as ethylamine and cocodimethylamine; substituted methanes such as di (2-hydroxy-ethoxy) methane, 5,5'-dichloro-2,2'-dihydroxydiphenylmethane, methylene-bisthiocyanate; 2,4,5,6 -Tetrachloro-1,3-benzenedicarbonitrile, 1,1-dichloro-N-((dimethylamino) -sulfonyl) -1-fluoro-N-phenylmethanesulfenamide, and 1-((diiodomethyl) sulfonyl) ) Substituted benzene such as -4-methylbenzene; tetraalkyl phosphonium halides such as tri-n-butyltetradecylphosphonium chloride; guanidine derivatives such as n-dodecylguanidine hydrochloride, bis- (dimethylthiocarbamoyl) -disulfide , Tetramethylthiuram disulfide; disulfides such as phenylcapsaicin; imidazole-containing compounds such as medetomidin; 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole and mixtures thereof. Is. Currently, preferably, the biocide is tin-free.

Currently, the preferred killing agents are 2,4,5,6-tetrachloroisophthalonitrile (chlorotalonyl), copper thiosocyanate (ferrous sulfosocyanate), N-dichloro-fluoromethylthio-N', N'-dimethyl. -N-phenylsulfamide (dichlorofluoranide), 3- (3,4-dichlorophenyl) -1,1-dimethylurea (diurone), N2-tert-butyl-N4-cyclopropyl-6-methylthio-1, 3,5-Triazine-2,4-diamine (cibutrin), 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, (2- (p-) Chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole; tralopyryl), cibutrin, (RS) -4- [1- (2,3-dimethylphenyl) ethyl] -3H-imidazole (medetomidin), 4,5-Dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT, Sea-Nine® 211N), dichloro-N-((dimethylamino) sulfonyl) fluor-N- (p-) Trill) methanesulphenamide (trilfluanide), 2- (thiocyanomethylthio) -1,3-benzothiazole ((2-benzothiazolylthio) methylthiocianate; TCMTB), triphenylboranpyridine (TPBP); bis (1-Hydroxy-2 (1H) -Pyridinethionate-0, S)-(T-4) Zinc (Zinc Pyridinethione; Zinc Pyrithione), Bis (1-Hydroxy-2 (1H) -Pyridinethionate-0 , S) -T-4) Copper (copper pyridinethione; copper pyrithion; copper omadin), zinc ethylene-1,2-bis-dithiocarbamate (zinc-ethylene-N-N'-dithiocarbamate; dineb), copper oxide It is selected from the group consisting of (I), metallic copper, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (diurone) and diiodomethyl-p-tolylsulfone; phenylcapsaicin. Preferably, at least one biocide is selected from the above list.

In a particularly preferred embodiment, the biocide is preferably selected from among biocides that are effective against soft stains such as mucus and algae. Examples of such killing agents are N2-tert-butyl-N4-cyclopropyl-6-methylthio-1,3,5-triazine-2,4-diamine (cibutrin), 4,5-dichloro-2-. n-octyl-4-isothiazolin-3-one (DCOIT, Sea-Nine® 211N), bis (1-hydroxy-2 (1H) -pyridinthionate-0, S)-(T-4) zinc (Zinc Pyridinethione; Zinc Pyridine), Bis (l-Hydridine-2 (1H) -Pyridinethionate-0, S) -T-4) Copper (Copper Pyridinethione; Copper Pyridine) and Zinc Ethylene-1,2- Bis-dithiocarbamate (zinc-ethylene-N-N'-dithiocarbamate); Dineb), bis (1-hydroxy-2 (1H) -pyridinethionate-0, S) -T-4) copper (copper pyridinethione) ; Copper pyridine; copper omazin). For hard fouling, copper (I) oxide, metallic copper, copper thiocyanate (copper sulfonate) can be used.

In a more particularly preferred embodiment, the biocide is an organic biocide, such as a pyrithione complex, such as zinc pyrithione, or, for example, copper pyrithione. Organic biocides are of organic origin, wholly or partially. Optionally, the marine antifouling agent may be encapsulated or adsorbed on an inert carrier or bound to another material to control its release.

The total amount of the organic killing agent in the antifouling composition of the present invention is 0.1% by weight to 40% by weight, for example 0.1% by weight to 20% by weight, for example 0.5% by weight to 10% by weight (coating). The dry weight of the composition), eg, in the range of 1% to 8% by weight. The total amount of inorganic biocides such as cuprous oxide, copper (I) oxide, and metallic copper in the antifouling composition of the present invention ranges from 0.5% to 80% by dry weight, for example, 1% to 70%. Can be. It will be understood that the amount of this ingredient will vary depending on the end use and the marine antifouling agent used.

To support the catalytic curing process, the coating compositions of the present invention may include a catalyst. WO 2014/131695 provides an extensive list of possible catalysts. Examples of catalysts that can be used are transition metal compounds, metal salts, and various metals such as tin, iron, lead, barium, cobalt, zinc, antimony, cadmium, manganese, chromium, nickel, aluminum, gallium, germanium and zirconium. Organic metal complex of. The salt is preferably a salt of a long chain carboxylic acid and / or a chelate or organometallic salt. Examples of suitable catalysts include, for example, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dibutyltin 2-ethylhexanoate, dibutyltin dineodecanoate, dibutyltin dimethoxydo, dibutyltin dibenzoate, dibutyl. Tin acetoacetate, dibutyltin acetylacetonate, dibutyltin alkylacetoacetate, dioctyltin dilaurate, dibutyltin octate, dioctyltin diacetate, dioctyltin 2-ethylhexanoate, dioctyltin dineodecanoate, dioctyltin Dimethoxydo, dioctyl tin dibenzoate, dioctyl tin acetoacetate, dioctyl tin acetyl acetonate, dioctyl tin alkyl acetoacetate, dimethyl tin dibutyrate, dimethyl tin bisneodecanoate, dimethyl tin didecanoate, tin naphthenate, tin butyrate, Tin oleate, tin caprylate, tin octanoate, tin stearate, tin octatoate, iron stearate, iron 2-ethylhexanoate, lead octanoate, lead 2-ethyloctanoate, cobalt 2-ethylhexanoate, Cobalt naphthenate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, zinc naphthenate, zinc stearate, metal triflate, triethyl tin tartrate, stannous octoart, carbomethoxyphenyl tin trisvelate, isobutyl tin triseroate Can be mentioned.

Further examples of suitable catalysts include organic bismuth compounds such as bismuth 2-ethylhexanoate, bismuth octanoate and bismuth neodecanoate. Further examples of suitable catalysts are organic titanium compounds, organic zirconium compounds and organic hafnium compounds, and titanium naphthenate, zirconium naphthenate, tetrabutyl titanate, tetrakis (2-ethylhexyl) titanate, triethanolamine titanate, tetra. (Isopropenyloxy) Titanate, Titanate Tetrabutate, Titanate Tetrapropanoate, Titanium Tetraisopropanate, Tetrabutyl Zirconate, Tetrax (2-ethylhexyl) Zirconic Acid, Triethanolamine Zirconate, Tetra (Isopropenyloxy) Zyrconic Acid , Titanates such as zirconium tetrabutanoate, zirconium tetrapropanoate, zirconium tetraisopropanoate and zirconic acid esters, as well as diisopropylbis (acetylacetonyl) titaniumate, diisopropylbis (ethylacetoacetonyl) titaniumate and diisopropylbis (ethylacetoacetonyl) titaniumate. Examples thereof include chelated titanates such as isopropoxybis (ethylacetacetate) titanate.

Preferably, the catalyst is present in an amount of 0.01% to 5% by weight, particularly 0.05% to 4% by weight, based on the total weight of the coating composition.

Solvents, Pigments, Fillers, Additives Coatings may contain solvents. Suitable solvents include aliphatic hydrocarbons, alicyclic and aromatic hydrocarbons, alcohols, ketones, esters, and mixtures thereof. Examples of suitable solvents are esters such as volatile oils, cyclohexane, toluene, xylene, naphtha solvents, methoxypropyl acetate, n-butyl acetate, 2-ethoxyethyl acetate octamethyltrisiloxane, and mixtures thereof. The solvent, if present, usually comprises 5% to 50% by weight based on the total weight of the coating composition. The solid content can be determined according to ASTM Method D2679.

The coating composition of the present invention may also contain pigments. Examples of pigments are black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide, carbon black, graphite, red molybdenate, yellow molybdenate, zinc sulfide, antimony oxide, sodium aluminum sulfosilicate, Kinacridone, Phthalocyanine Blue, Phthalocyanine Green, Indantron Blue, Aluminum Cobalt Oxide, Carbazole Dioxazine, Chromium Oxide, Isoindoline Orange, Bisacetoacetotridiol, Benzimidazolone, Kinoftalone Yellow, Isoindoline Yellow, Tetrachloroisoindolinone, Kinoftalone yellow, metal flake materials (eg aluminum flakes) or other so-called barrier pigments or rust-preventive pigments such as zinc powder or zinc alloys, or other so-called lubricant pigments such as graphite, molybdenum disulfide, tungsten disulfide or boron nitride. Be done. Preferred pigments are black iron oxide, red iron oxide, yellow iron oxide, sodium aluminum sulfosilicate and titanium dioxide.

The proportion of pigment can range from 0% to 25% by weight, preferably from 0% to 15% by weight, based on the total weight of the coating composition.

The coating composition of the present invention may also contain a filler. Examples of fillers that can be used in the coating compositions according to the invention are silica or silicates (eg, talc, feldspar, and kaolin) containing zinc oxide, barium sulphate, calcium sulphate, calcium carbonate, calcined silica, bentonite, and other clays. ), And a solid silicone resin that is generally a condensed branched polysiloxane. Some fillers, such as fumed silica, may have a thixotropy effect on the coating composition. The percentage of filler is in the range of 0% to 25% by weight, preferably in the range of 0% to 10% by weight, more preferably in the range of 0% to 5% by weight, based on the total weight of the coating composition. Can be.

The coating composition according to the invention optionally comprises one or more components selected from other surfactants, wetting agents, thickeners, anti-settling agents, and dyes.

Additional binders can be used to adjust the self-polishing and mechanical properties of the coating film. Examples of binders that can be used in addition to the binder of the present invention in the coating composition of the present invention include other polysiloxanes.

Application of Coating Composition The coating composition of the present invention can be applied to all or part of the surface of any object that is susceptible to fouling. The surface may be permanently or intermittently below the surface (eg, through tide movements, various loading operations, or expansion). The surface of an object is usually the hull of a ship, or the surface of a fixed marine object such as an oil platform or buoy. Application of the coating composition can be achieved by any convenient means, such as painting (eg, using a brush or roller) or spraying the coating onto an object. Generally, the surface needs to be separated from seawater to allow coating. The application of the coating can be achieved as conventionally known in the art.

The coating composition can be applied by conventional techniques such as brushing, roller coating, or spraying (airless and air assist). It is preferable to apply the coating composition to the primed substrate in order to achieve proper adhesion to the substrate. The primer can be any conventional primer / sealer coating system suitable for PDMS coating. It is also possible to apply the coating composition according to the invention on a substrate containing an old antifouling coating layer or fouling release layer. Before the coating composition according to the invention is applied to such an old layer, the old layer is washed by high pressure water washing to remove fouling. The primers disclosed in WO 99/33927 can be used as a tie coat between the old coating layer and the coating composition according to the invention.

Optionally, the primer may contain an adhesion promoter disclosed in WO 2010/018164.

Optionally, the primer may include a biocide. The coating can be soaked immediately after curing, providing immediate antifouling or fouling release protection. As mentioned above, the coating composition according to the invention has very good antifouling and fouling release properties. This makes these coating compositions very suitable for use as antifouling or fouling release coatings for marine applications. Coatings include dynamic and static structures such as hulls, buoys, drilling platforms, dry dock equipment, oil and / or gas production rigs, floating oil and gas processing, storage and unloading vessels, aquatic equipment, nets. And cages, energy generators such as offshore wind turbines and tide and wave energy devices, cooling water intakes for power plants, pipes submerged in water, and tanks, pipes and conduits used to store and transport water. Can be used for. The coating can be applied to any substrate used for these structures, for example metal, concrete, wood, plastic, fiber reinforced plastic.

Hereinafter, the present invention will be defined with reference to the following non-limiting examples.

Determining the Molar Mass Distribution of Polymers Polymers are characterized by gel permeation chromatography (GPC) measurements. Equipment details:
a. Tetrahydrofuran as mobile phase:
Molecular Weight Distribution (MWD) is ambient using a Polymer Laboratories PL-GPC 50 instrument with two PLgel 5 μm Mixed-D columns (300 x 7.5 mm) from Polymer Laboratories and a refractive index (RI) detector as an eluent. Continuous measurements were made at temperature and constant flow rate of 1 mL / min. Columns were calibrated using polystyrene standard Easyvials PS-M from Polymer Laboratories. Data were processed using Cirrus software from Polymer Labs.

b. Toluene as mobile phase:
The molecular weight distribution (MWD) is determined using toluene as an eluent using an EcoSEC instrument with a Micro SDV column (1000/10000 Å, length 55 cm, inner diameter 0.4 cm) from Tosoh Bioscience GmbH and a refractive index (RI) detector. It was used and measured at a constant flow rate of 0.35 mL / min at a temperature of 35 ° C. Columns were calibrated using polystyrene standards from PSS (162 g / mol to 2.52 million g / mol).

Samples were prepared by dissolving the amount of polymer solution corresponding to 5 mg of dry polymer in 5 mL of tetrahydrofuran or toluene. Samples were maintained at room temperature for a minimum of 4 hours prior to sampling for GPC measurements.
Weight average molecular weight (Mw), number average molecular weight (Mn), and Mw / Mn corresponding to the degree of dispersion (D _M) has been reported.

chemicals:
Alpha, omegaaminosiloxane [Tegomer A-Si 2122 (n = 10) or Tegomer A-Si2322 (n = 30)], bis [3- (trimethoxysilyl) propyl] amine (registered trademark) available from Evonik. ) 1124), alpha, omegahydroxyalkylsiloxane (Tegomer® H-Si2515).

Methyl 5-hexenoate available from TCI EUROPE GmbH, nonanediol diacrylate, titanium (IV) -butoxide, dibutyltin dilaurate, available from Sigma-Aldrich, 1,8-diaza-7-bicyclo [5.4. 0] Undecene (DBU), dimethyltin dichloride, p-toluenesulfonic acid.

Methacryloxypropyl-terminated polydimethylsiloxane monomer, vinyl-terminated polydimethylsiloxane, (3-mercaptopropyl) trimethoxysilane, acrylicoxy-terminated ethylene oxide-dimethylsiloxane-ethylene oxide available from ABCR Chemicals. A (mercaptopropyl) methyl-terminated siloxane available from GP silicones.

1,8-octanedithiol, succinic anhydride, allyl alcohol, benzoquinone, 2,2'-azobis (2-methylpropionitrile), triethylamine, succinic acid, 2-mercaptoethanol, diethylene glycol mono, available from Sigma-Aldrich Allyl ether, hexamethylenediamine, dimethyl succinate, 2- (methylamino) ethanol, xylene anhydride, methylene dichloride anhydride, dioxane anhydride.

[Example]
Example 1a: Thiol-en-Michael addition reaction: General scheme

R "= H or CH ₃
In a multi-neck flask with a nitrogen line, stirrer and internal thermometer, methacryloxypropyl-terminated polydimethylsiloxane (DMS-R18, CAS No. 58130-03-3, ABCR Chemicals) (100 g, 0.04 eq), Anhydrous 1,8 octanedithiol (14.58 g, 0.04 eq) and 1,8-diaza-7-bicyclo [5.4.0] undecene (DBU) (0.115 g, 0.1 wt%). Dissolved in xylene.

The mixture was stirred at 30 ° C. for 3 hours under a nitrogen atmosphere. Xylene and all volatiles were removed by vacuum distillation (3 hours, 80 ° C, <1 mbar).
GPC data: Mw9246 g / mol, Mn4020 g / mol, MWD2.3 (toluene, PS standard, 35 ° C)

Example 1b:
In a multi-neck flask with a nitrogen line, stirrer and internal thermometer, methacryloxypropyl-terminated polydimethylsiloxane (DMS-R18, CAS No. 58130-03-3, ABCR Chemicals) (150 g, 0.01182 mol, vinyl), 1,6 hexanedithiol (2.49 g, 0.016 mol) and 1,8-diaza-7-bicyclo [5.4.0] undecene (DBU) (0.15 g, 0.1 wt%) were mixed. The reaction mixture was stirred under vacuum (100 mbar) at 70 ° C. for 10 hours.
GPC data: Mw11264 g / mol, Mn5587 g / mol, MWD2.02 (toluene, PS standard, 35 ° C)

Example 2a
Synthesis of functionalized diesters: general scheme

In a multi-neck flask with a nitrogen line, stirrer and internal thermometer, succinic anhydride (50 g, 0.5 mol), allyl alcohol (87 g, 1.5 mol), benzoquinone (0.05 g) and titanium (IV) butoxide ( 0.1 g) was dissolved in anhydrous xylene:

The mixture was stirred at 120 ° C. for 8 hours under quiet nitrogen atmosphere stripping conditions. Xylene and residual alcohol were removed by vacuum distillation (3 hours, 80 ° C, 10 mbar).

Example 2b

In a multi-neck flask with a nitrogen line, stirrer and internal thermometer, a, w- (mercaptopropyl) dimethylsiloxane (100 g, 0.026 mol-SH functionality), diallyl succinate (12.29, 0.062 mol). ) And 2,2'-azobis (2-methylpropionitrile) (100 mg) were dissolved in xylene anhydride. The mixture was stirred at 70 ° C. for 5 hours under a nitrogen atmosphere. Xylene and residual volatiles were removed by vacuum distillation (3 hours, 80 ° C, 10 mbar).

Example 3a General scheme of siloxane-ene + thiol-terminated ester

Succinic acid (100 g, 0.931 mol), 2-mercaptoethanol (77.27 g, 1 mol) and dimethyltin dichloride (0.05 wt%) anhydrous in a multi-neck flask with a nitrogen line, stirrer and internal thermometer. Dissolved in xylene:

The mixture was stirred under nitrogen at 120 ° C. for 5 hours. Xylene was removed by vacuum distillation at 120 ° C. <50 mbar.

Example 3b-One-pot synthesis In a multi-neck flask with a nitrogen line, stirrer and internal thermometer, vinyl-terminated polydimethylsiloxane (DMS-V03, CAS.68083-19-2, ABCR Chemicals) (100 g, 0.0133 mol). , Bis (2-mercaptoethyl) succinate (3.35 g, 0.0133 mol), (3-mercaptopropyl) trimethoxysilane (0.19 g, 0.001 mol) and 2,2'-azobis (2-methyl) Propionitrile (100 mg) was dissolved in xylene anhydride. The mixture was stirred at 70 ° C. for 3 hours under a nitrogen atmosphere. Xylene was removed by vacuum distillation (3 hours, 80 ° C., <1 mbar).
GPC data: Mw23565 g / mol, Mn7601 g / mol, MWD3.1 (toluene, PS standard, 35 ° C)

Example 3c.
In a multi-neck flask equipped with a nitrogen line, stirrer and internal thermometer, 50 mL of anhydrous xylene was added to the flask. The temperature of xylene was maintained at 75 ° C. under a nitrogen atmosphere. In a dropping funnel, α, ω-vinyl-terminated polydimethylsiloxane (CAS.68083-19-2, ABCR Chemicals) (100 g, 0.04 mol), 1,6 hexanedithiol (6 g, 0.04 mol), vinyl trimethoxysilane (1.48 g, 0.01 mol) was mixed. In another dropping funnel, 2,2-azodi (2-methylbutyronitrile) (AMBN) (500 mg) is dissolved in 10 mL of anhydrous xylene. The reaction mixture and the initiator solution were added dropwise to the xylene solution at 75 ° C. for 2 hours. The mixture was stirred at 75 ° C. for an additional 3 hours under a nitrogen atmosphere. Then, xylene was removed by vacuum distillation (3 hours, 80 ° C., <1 mbar).
GPC data: Mw29056g / mol, Mn8726g / mol, MWD3.33 (toluene, PS standard, 35 ° C)

Example 3d:
In a multi-neck flask equipped with a nitrogen line, stirrer and internal thermometer, 50 mL of anhydrous xylene was added to the flask. The temperature of xylene was maintained at 75 ° C. under a nitrogen atmosphere. In a dropping funnel, α, ω-vinyl-terminated polydimethylsiloxane (CAS.68083-19-2, ABCR Chemicals) (65 g, 0.026 mol), a, w- (mercaptopropyl) dimethylsiloxane (GP silicones 100 g, 0. 026 mol, -SH functionality) and vinyltrimethoxysilane (1.92 g, 0.013 mol) were mixed. In another dropping funnel, 2,2-azodi (2-methylbutyronitrile) (AMBN) (500 mg) is dissolved in 10 mL of anhydrous xylene. The reaction mixture and the initiator solution were added dropwise to the xylene solution at 75 ° C. for 2 hours. The mixture was stirred at 75 ° C. for an additional 3 hours under a nitrogen atmosphere. Then, xylene was removed by vacuum distillation (3 hours, 80 ° C., <1 mbar).
GPC data: Mw36,029 g / mol, Mn10,722 g / mol, MWD 3.36 (toluene, PS standard, 35 ° C)

Example 4-General scheme

Example 4a
In a multi-neck flask with a nitrogen line, stirrer and internal thermometer, acrylic oxy-terminated ethylene oxide-dimethylsiloxane-ethylene oxide (ABA block copolymer) (DBE-U22, CAS.117440-21-9, ABCR Chemicals) (100 g). , 0.058 mol), bis (2-mercaptoethyl) succinate (14.01 g, 0.0058 mol), (3-mercaptopropyl) trimethoxysilane (1.12 g, 0.006 mol) and 1,8 -Diaza-7-bicyclo [5.4.0] Undecene (DBU) (0.126 g, 0.1% by weight) was dissolved in xylene anhydride. The mixture was stirred at 40 ° C. for 3 hours under a nitrogen atmosphere. Xylene was removed by vacuum distillation (3 hours, 80 ° C., <1 mbar).
GPC data: Mw20987 g / mol, Mn7442 g / mol, MWD2.82 (toluene, PS standard, 35 ° C)

Example 4b:
In a multi-neck flask equipped with a nitrogen line, stirrer and internal thermometer, 50 mL of anhydrous xylene was added to the flask. The temperature of xylene was maintained at 75 ° C. under a nitrogen atmosphere. In a dropping funnel, acrylicoxy-terminated ethylene oxide-dimethylsiloxane-ethylene oxide (ABA block copolymer) (DBE-U22, CAS.117440-21-9, ABCR Chemicals) (100 g, 0.058 mol), 1,6 hexanedithiol ( 8.72 g, 0.058 mol) and vinyltrimethoxysilane (4.29 g, 0.029 mol) were mixed. In another dropping funnel, 2,2-azodi (2-methylbutyronitrile) (AMBN) (500 mg) is dissolved in 10 mL of anhydrous xylene. The reaction mixture and the initiator solution were added dropwise to the xylene solution at 75 ° C. for 2 hours. The mixture was stirred at 75 ° C. for an additional 3 hours under a nitrogen atmosphere.

GPC data: Mw40,524 g / mol, Mn 6,484 g / mol, MWD 6.25 (THF, PS standard, 35 ° C)

Example 5a General scheme of siloxane-thiol + allyl-terminated diester

Succinic anhydride (50 g, 0.5 mol), diethylene glycol monoallyl ether (146.18 g, 1 mol) and titanium (IV) butoxide (0.1 g) in a multi-neck flask with a nitrogen line, stirrer and internal thermometer. Dissolved in xylene anhydride:

The mixture was stirred under a nitrogen atmosphere at 120 ° C. for 4 hours. Xylene and all volatiles were removed by vacuum distillation (3 hours, 80 ° C, 40 mbar).

Example 5b General scheme

A multi-neck flask with a nitrogen line, stirrer and internal thermometer, a, w- (mercaptopropyl) dimethylsiloxane copolymer (GP silicones, 100 g, 0.026 mol-SH functionality), bis (2- (allyloxy). ) Ethyl) succinate (10.03 g, 0.036 mol), (3-mercaptopropyl) trimethoxysilane (1.87 g, 0.01 mol) and 2,2'-azobis (2-methylpropionitrile) ( 100 mg) was dissolved in anhydrous xylene. The mixture was stirred at 70 ° C. for 5 hours under a nitrogen atmosphere. Downstream xylene and volatiles were removed by vacuum distillation (3 hours, 80 ° C, 1 mbar).
GPC data: Mw23853 g / mol, Mn8085 g / mol, MWD 2.95 (toluene, PS standard, 35 ° C)

Example 6: General scheme of siloxane-thiol + (meth) acrylic terminal ester

In a multi-neck flask with a nitrogen line, stirrer and internal thermometer, a, w- (mercaptopropyl) dimethylsiloxane polymer (GP silicones 100 g, 0.026 mol-SH functionality), nonanediol diacrylate (CAS-Nr. : 107481-28-7, TCI polymers, 9.66 g, 0.036 mol), (3-mercaptopropyl) trimethoxysilane (1.87, 0.01 mol) and 1,8-diaza-7-bicyclo [5. 4.0] Undecene (DBU) (0.109 g, 0.1 wt%) was dissolved in xylene anhydride. The mixture was stirred at 30 ° C. for 5 hours under a nitrogen atmosphere. Xylene and other volatiles were removed by vacuum distillation (2 hours, 80 ° C., 70 mbar).
GPC data: Mw22643 g / mol, Mn7522 g / mol, MWD3.01 (toluene, PS standard, 35 ° C)

Example 7
(Meta) Acrylate and Amine Functional Monomers-Michael Addition Reaction-General Scheme

In a multi-neck flask with a nitrogen line, stirrer and internal thermometer, methacryloxypropyl-terminated polydimethylsiloxane (DMS-R18, CAS No. 58130-03-3, ABCR Chemicals) (150 g, 0.0118 mol, vinyl), Hexamethylenediamine (1.37 g, 0.0118 mol) and 1,8-diaza-7-bicyclo [5.4.0] undecene (DBU) (0.15 g, 0.1 wt%) were mixed. The mixture was stirred under vacuum at 100 mbar at 70 ° C. for 12 hours.
GPC data: Mw11449 g / mol, Mn5030 g / mol, MWD 2.28 (toluene, PS standard, 35 ° C)

Example 8-General scheme

Tegomer® A-Si2322 (100 g, 0.038 mol), diallyl succinate (7.53 g, 0.038 mol), and 1,8 in a multi-neck flask with a nitrogen line, stirrer and internal thermometer. -Diaza-7-bicyclo [5.4.0] Undecene (DBU) (270 mg, 0.25 wt%) was dissolved in xylene anhydride. The mixture was stirred at 30 ° C. for 3 hours under a nitrogen atmosphere. Xylene was removed by vacuum distillation (3 hours, 80 ° C., <1 mbar).
GPC data: Mw7449 g / mol, Mn3513 g / mol, MWD2.12 (toluene, PS standard, 35 ° C)

Example 9 General scheme of PDMS-acrylate + amine-terminated ester

Dimethyl succinate (50 g, 0.34 mol), 2- (methylamino) ethanol (10.94 g, 1.02 mol) and p-toluenesulfonic acid (50 g, 0.34 mol) in a multi-neck flask with a nitrogen line, stirrer and internal thermometer. 0.1 g) was dissolved in xylene. The mixture was stirred at 120 ° C. for 4 hours in a nitrogen stripping atmosphere to remove the reaction water. Xylene and other volatiles (excess alcohol) were removed by vacuum distillation (4 hours, 90 ° C, <1 mbar).
GPC data: Mw5449 g / mol, Mn2162 g / mol, MWD2.52 (toluene, PS standard, 35 ° C)

Example 9b-General scheme-One-pot synthesis

In a multi-neck flask with a nitrogen line, stirrer and internal thermometer, methacryloxypropyl-terminated polydimethylsiloxane (DMS-R18, CAS No. 58130-03-3, ABCR Chemicals) (100 g, 0.022 mol), bis ( 2- (Methylamino) ethyl) succinate (5.16 g, 0.022 mol), bis [3- (trimethoxysilyl) propyl] amine (Dynasylan® 1124) (1.72 g, 5 mmol) and 1 , 8-Diaza-7-bicyclo [5.4.0] Undecene (DBU) (0.270 g, 0.25 wt%) was dissolved in xylene anhydride. The mixture was stirred at 30 ° C. for 3 hours under a nitrogen atmosphere. Xylene and all other volatiles were removed by vacuum distillation (4 hours, 40 ° C, <1 mbar).
GPC data: Mw13954 g / mol, Mn4828 g / mol, MWD 2.89 (toluene, PS standard, 35 ° C)

Example 10: PDMS-acrylate + PDMS-amine

Multi-neck flask with nitrogen line, stirrer and internal thermometer, methacryloxypropyl-terminated polydimethylsiloxane (DMS-R18, CAS No. 58130-03-3, ABCR Chemicals) (100 g, 0.022 mol), Tegomer ( Registered Trademarks) A-Si2322 (57.7 g, 0.022 mol), Bis [3- (trimethoxysilyl) propyl] amine (Dynasylan® 1124) (1.97, 0.006 mol) and 1,8- Diaza-7-bicyclo [5.4.0] undecene (DBU) (0.394 g, 0.25 wt%) was dissolved in xylene anhydride. The mixture was stirred at 30 ° C. for 3 hours under a nitrogen atmosphere. Xylene and volatiles were removed by vacuum distillation (4 hours, 40 ° C., <0.1 mbar).
GPC data: Mw12567 g / mol, Mn4175 g / mol, MWD3.01 (toluene, PS standard, 35 ° C)

Example 11: Film forming experiment: A PDMS-based resin (Example 3c) was cured with 0.5 wt% TIB Kat 318 at room temperature. The neat resin was applied onto the glass slides using a film applicator (Simex GmbH). The thickness of the wet film was 300 μm. The film was formed in 24 hours.

Claims (30)

A fouling-release coating composition comprising a bus Indah and at least one additive oil,
A coating composition in which the binder comprises a polymer containing a polysiloxane group, a plurality of ester groups, and a plurality of thio groups, amino groups or disulfide groups. An antifouling coating composition comprising a binder and at least one marine antifouling agent.
A coating composition in which the binder comprises a polymer containing a polysiloxane group, a plurality of ester groups, and a plurality of thio groups, amino groups or disulfide groups. The coating composition according to claim 1, which does not contain a biocide. The binder contains a plurality of polysiloxane groups, a plurality of ester groups, a plurality of thio groups ( represented by the formula CH _2- S—CH ₂ −), and an amino group (formula CH _2- NRa-CH) in its skeleton. ₂ - is represented by, Ra comprises a polymer containing H or _{C 1-6} alkyl group Ru der) or S-S group,
The coating composition according to claim 1 or 2. The binder comprises a polymer having a plurality of polydimethylsiloxane groups, a plurality of ester groups, and a repeating unit containing a plurality of thio groups, amino groups or SS groups in its backbone.
The coating composition according to claim 1 or 2. Wherein the binder comprises a vinyl terminated polysiloxane polyester monomer, the reaction product of a bi scan thiol monomer or bis-amino monomers,
The coating composition according to claim 1 or 2. The binder comprises a reaction product of a thiol-terminated polysiloxane monomer and a vinyl-terminated polyester monomer or a thiol-terminated polyester monomer.
The coating composition according to claim 1 or 2. The binder comprises a reaction product of a vinyl-terminated polysiloxane monomer and a thiol-terminated polyester monomer.
The coating composition according to claim 1 or 2. The binder comprises a reaction product of an amino-terminal polysiloxane monomer and a vinyl-terminal polyester monomer.
The coating composition according to claim 1 or 2. The vinyl group forms part of the (meth) acryloxyalkyl group.
The coating composition according to claims 6 to 9. Comprising a thiol-terminated polysiloxane polyester monomer, the reaction product of thiols terminal monomer,
The coating composition according to claim 1 or 2. General formulas (A1) to (A2):

(In the formula, each R ₁ is the same or different, unsubstituted or substituted C _1-20 alkyl group, C _2-20 alkenyl group, C _3-20 cycloalkyl group, C _6-20 aryl group, C _7-20. Represents an arylalkyl group, or polyoxyalkylene chain;
X and Y may be different even in the _{same, -CR = CH 2, - (} CR "2) x '-CR = CH 2, - (CR" 2) x' -CR "2 -OCO _{-CR = CH 2, -CR "2} -OCO-CR = CH 2, - (CR" 2) x '-SH, - (CR "2) x' -O- (CR" 2) x '-SH, -(CR " ₂ ) _x- [O- (CR" ₂ ) _x' ] _f- OCO-CR = CH ₂ ,-(CR " ₂ ) _x' -(OR ⁸ ) _a- (OR ⁸ ) _b- OR ^7- SH,-(CR " ₂ ) _x' -(OR ⁸ ) _a- (OR8) _b- OR ⁷ -CR = CH ₂ , -CR" _2- Ar-CR " _2- SH,-(CR" _{2 ) x 'C≡CH, - (CR} "2) x' -O- (CR" 2) x '- (CHOH) - (CR "2) x -OCO-CR = CH 2 or - _(CR" 2) _x' -(OR ⁸ ) _a- (OR ⁸ ) _b- OR ⁷ Represents C≡CH;
"R" is independently a C _1-6 alkyl group or H ;
x 'is 1 from 1 0;
Each R is independently H or Me;
Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, a = 0 to 50, b = 0 to 50, and a + b = 1 to 50;
f is 1 to 50;
Ar _is an _{C 6-12} aryl group; and n is from 1 to 50 0;
Or, n '+ m is from 1 by adding 50 0. ) With at least one polysiloxane monomer A',
Formula HS-Q3-SH (BI)
(In the formula, Q3 is C _2-20 alkyl group, C _3-20 cycloalkyl group, phenyl group, biphenyl group, terphenyl group, C _7-20 alkyl aryl group, alkyl-polysiloxane-alkyl, C _{4- 20} alkylcycloalkyl group or polyether;
Wherein said _{C 2-20} alkyl _{group, C 3-20 cycloalkyl, C 7-20} alkylaryl group or a _{C 4-20} alkylcycloalkyl group, may include one or more of O, N, S, or P or al Arbitrarily contains selected heteroatoms;
However, the SH group in the monomer B'reacts with the X and Y groups of the ester containing the monomer A'to form the group C—S—CH ₂ or SS group. )
At least one second monomer B'
Or formula (BII) or (BIII)

(In the formula, Q1 is a covalent bond, C _1-20 alkyl group, C _3-10 cycloalkyl group, C _3-10 cycloalkenyl group, C _6-10 aryl group, C _7-12 aryl alkyl group, formula R. ^{_{7 - (oR 8) a -}} (oR 8) polyoxyalkylene chain of _{^{b -OR 7, -Ph-O-}} C 1-6 alkyl -OPh-, represents a heterocyclyl group, or a _{C 4-10} alkyl radical;
Wherein said _{C 1-20} alkyl _{group, C 3-10} cycloalkyl group or a _{C 3-10} cycloalkenyl group, comprises one or more O, N, heteroatoms selected either S or P et optionally ;
L is 1 or more, for example O from 1 4, N, _{C 1-20} alkylene group, optionally containing S or P or we selected the heteroatom or the formula:
− (OR ⁸ ) _a − (OR ⁸ ) _b − OR ^{7 −}
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, respectively, and a = 0 to 50, b = 0 to 50 and a + b = 1 to 50;
R is H or Me. )
Is a polyoxyalkylene chain of
Q2 is a covalent bond, a C _1-20 alkyl group, a C _3-10 cycloalkyl group, a C _2-6 aminoglycol, a C _2-6 thioglycol, or a C _6-10 aryl group, wherein the C is here. _1-20 alkyl _{group, C 3-10} cycloalkyl group or a _{C 3-10} cycloalkenyl group, may optionally include one or more O, N, S, or P or we selected the heteroatoms;
W and _{Z, -SH, - (CR "2} ) x 'SH, CH 2 = CR-, CH 2 = CR- (CR" 2) x' -, - C≡CH, -NHCH 2 -CR = CH ₂ , NHCH _2- CR≡CH-NHRa, -NHRa, or W and Z = CH ₂ (thus forming a double bond with the C atom to which W / Z is attached);
Ra is H or _{C 1-6} alkyl group, wherein said alkyl group contains O on one or more, N, S or P or we selected the heteroatom optionally;
"R" is independently a C _1-6 alkyl group or H ;
x 'is 1 from 1 0;
Ra is H or _{C 1-6} alkyl group, wherein said alkyl group contains O on one or more, N, S or P or we selected the heteroatom optionally;
However, the W and Z groups in the monomer B'react with the X and Y groups in the monomer A'to form the group C—S—CH ₂ , amino group or SS group. )
At least one second monomer B'
Or formula:
HRaN-Q5-NHRa (DI)
(In the formula, Q5 is a C _2-20 alkyl group, a C _2-20 alkenyl group, a C _3-20 cycloalkyl group, a phenyl group, a biphenyl group, a terphenyl group, Ph-O-Ph, C _7-20 alkyl. aryl group, an alkyl - polysiloxane - _{alkyl, C 4-20} alkylcycloalkyl _group, a _{C 3-10} heterocyclic group or polyether le, wherein said _{C 2-20} alkyl _{group, C 3-20} cycloalkyl group , _{C 7-20} alkylaryl group or a _{C 4-20} alkylcycloalkyl group, includes O on one or more, N, S or P or we selected the heteroatom optionally;
Ra is an H or C _1-6 alkyl group;
However, the NRaH group in the monomer D'reacts with the X and Y groups of the ester containing the monomer A'to form the group C-NRa-CH ₂ . )
At least one second monomer D'
Binder for coating compositions containing reaction products with. General formulas (C1) to (C2):

(In the formula, each R ₁ is the same or different, unsubstituted or substituted C _1-20 alkyl group, C _2-20 alkenyl group, C _3-20 cycloalkyl group, C _6-20 aryl group, C _7-20. Represents an arylalkyl group, or polyoxyalkylene chain;
X and Y may be different even in the _{same, - (CR "2) x} '-NRaH, - (CR" 2) x' -NH- (CR "2) x '-NRaH, - ( _{CR "2) x '- (} O-C2-6 _{alkyl) x' -NRaH, - (CR} " 2) x '-O- (CR "2) x' -NRaH or _-CR," 2 -Ar-CR " _{Represents 2-} NRaH;
"R" is independently a C _1-6 alkyl group or H;
Ra is an H or C _1-6 alkyl group;
x'is 1 to 10; and n is 1 to 500;
Alternatively, n'+ m is 1 to 500 in total. )
At least one polysiloxane monomer C'and formula (BX) or (BXI)

(In the formula, Q1 is a covalent bond, C _1-20 alkyl group, C _3-10 cycloalkyl group, C _3-10 cycloalkenyl group, C _6-10 aryl group, C _7-12 aryl alkyl group, formula R. ^{_{7 - (oR 8) a -}} (oR 8) b -OR 7 -Ph-O-C 1-6 alkyl -OPh-, represents a polyoxyalkylene chain heterocyclyl group, or a _{C 4-10} alkyl radical;
Here, the C _1-20 alkyl group, C _3-10 cycloalkyl group, or C _3-10 cycloalkenyl group optionally contains a heteroatom selected from one or more O, N, S or P;
L is a C1-20 alkylene group optionally containing a heteroatom selected from one or more O, N, S or P, or formula:
− (OR ⁸ ) _a − (OR ⁸ ) _b − OR ^{7 −}
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, respectively, and a = 0 to 50, b = 0 to 50, and a + b = 1 to 50). It is a chain;
R is H or Me;
Q2 is a covalent bond, a C _1-20 alkyl group, a C _3-10 cycloalkyl group, a C _2-6 aminoglycol, a C _2-6 thioglycol, or a C _6-10 aryl group, wherein the C is here. _1-20 alkyl _{group, C 3-10 cycloalkyl, C 3-10} cycloalkyl groups include O on one or more, N, S or P or al heteroatom optionally chosen;
W and Z _{are, CH 2 = CR-, CH 2} = CR-CH 2 -, NHCH 2 -CR = CH 2, a -C≡CH, or W and Z, = CH ₂ (therefore, W / Z Form a double bond with the C atom to which it is bonded);
However, the W and Z groups in the monomer B'react with the amino X and Y groups in the monomer C'to form the group C-NRa-CH ₂ . )
A binder for a coating composition containing a reaction product with at least one second monomer B'. Monomer A'is the formula (A5):

(In the equation, X and Y are the same, −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH = CH ₂ , − (CH ₂ ) _{x ′} −CH ₂ −OCO −CH = CH ₂ , _{-CH 2 -OCO-CH = CH 2} , - (CH 2) x '-CH 2 -OCO-CMe = CH 2, -CH 2 -OCO-CMe = CH 2, - (CH 2) x' -O- _{(CH 2) x '- (} CHOH) - (CH 2) x -OCO-CR = CH 2 or - _(CH 2) _x' represents -SH;
x 'is 1 1 0; is and n, it is from 10 30 0. ) It expresses in,
The binder according to claim 12 . Monomer A'is the formula (A6):

(In the formula, each R ₁ is a methyl group,
X and Y are the _{same, -CH = CH 2, - (} CH 2) x '-CH = CH 2, - (CH 2) x' -CH 2 -OCO-CH = CH 2, -CH 2 - _{OCO-CH = CH 2, -} (CH 2) x '-CH 2 -OCO-CMe = CH 2, -CH 2 -OCO-CMe = CH 2, - (CH 2) x' represents -SH;
x'is 1 to 5; and n is 15 to 15 to 300. ) It expresses in,
The binder according to claim 12 . Monomer A'is the formula (A7):

(In the formula, each R ₁ is a methyl group,
X and Y are the _{same, -CH = CH 2, - (} CH 2) x '-CH = CH 2, - (CH 2) x' -CH 2 -OCO-CH = CH 2, -CH 2 - _{OCO-CH = CH 2, -} (CH 2) x '-CH 2 -OCO-CMe = CH 2, -CH 2 -OCO-CMe = CH 2, - (CH 2) x' represents -SH x 'is 1 to 5 ; and n is 15 to 100. ),
The binder according to claim 12. Monomer B'is
HS-Q3-SH (BIV)
(In the formula, Q3 represents a C _2-16 alkylene group, an alkyl-polysiloxane-alkyl, or a polyether group.)
Represented by,
The binder according to claim 12. Monomer B'is of formula BV or BVI

(In the formula, Q1 is a C _2-10 alkyl group, a C _3-8 cycloalkyl group, a C _3-8 cycloalkenyl group, a C _6-10 aryl group, a C _7-12 aryl alkyl group, or a C _4-10. Alkylcycloalkyl group;
Q2 is a covalent bond, a C _1-10 alkyl group, a C _3-8 cycloalkyl group, a C _2-6 aminoglycol, a C _2-6 thioglycol, or a C _6-10 aryl group;
R is Me or H;
L is, _{C 1-10} alkylene Motoma or expression:
^{_{- (OR 8) a OR 7}} -
(Here, R ⁷ and R ⁸ are independently C _2-6 alkylene groups, and a = 0 to 50, respectively) are polyoxyalkylene chains;
W and Z are -SH, -CH _2- SH, CH ₂ = CR-, CH ₂ = CR-CH _2- , or W and Z are = CH ₂ . ) Polyoxyalkylene chain. ) It expresses in,
The binder according to claim 12 . Monomer B'is the formula BX

(In the formula, Q1 is a C _2-10 alkyl group, a C _3-8 cycloalkyl group, a C _3-8 cycloalkenyl group, a C _6-10 aryl group, a C _7-12 aryl alkyl group, or a C _4-10. Alkylcycloalkyl group;
R is Me or H;
L is, _{C 1-10} alkylene Motoma or expression:
^{_{- (OR 8) a OR 7}} -
(Here, R ⁷ and R ⁸ are independently C _2-4 alkylene and a = 0 to 50), which is a polyoxyalkylene chain;
W and Z are -SH, -CH _2- SH, CH ₂ = CR-, CH ₂ = CR-CH _2- , or W and Z are = CH ₂ . )
Represented by,
The binder according to claim 12. Monomer C'is

(X and Y groups are the _{same, - (CH 2) x '} -NH 2, - (CH 2) x' -NH- (CH 2) x '-NH 2, - (CH 2) x' _{-O- (CH 2) x '-NH} 2, - (CH 2) x' -O- (CH 2 CH (CH 3)) x ' be -NH _2;
x 'is located from 1 to 5; and n is from 1 to 50 0. )
Represented by,
The binder according to claim 13. Monomer D'is of formula HRaN-Q5-NHRa (DII)
(In the formula, Q5 is a C _2-10 alkyl group, C _1-6 alkyl-polysiloxane-C _1-6 alkyl;
Ra is an H or C _1-6 alkyl group. ),
Alternatively, the monomer B'is of formula BVIII.

(In the formula, Q1 is a C _2-10 alkyl group, a C _3-8 cycloalkyl group, a C _3-8 cycloalkenyl group, a C _6-10 aryl group, a C _7-12 aryl alkyl group, or a C _4-10. Alkylcycloalkyl group;
L is, _{C 1-10} alkylene Motoma or expression:
^{_{- (OR 8) a OR 7}} -
(Here, R ⁷ and R ⁸ are independently C _2-4 alkylene groups, and a = 0 to 50, respectively).
Ra is an H or C _1-6 alkyl group. )
Represented by,
The binder according to claim 12. Monomer B'is the formula (BXXI)

(In the formula, Q1 is a C _2-10 alkyl group, a C _3-8 cycloalkyl group, a C _3-8 cycloalkenyl group, a C _6-10 aryl group, a C _7-12 aryl alkyl group, or a C _4-10. Alkylcycloalkyl group;
L is, _{C 1-10} alkylene Motoma or expression ^{_{- (OR 8) a OR 7}} -
(Here, R ⁷ and R ⁸ are independently C _2-4 alkylene groups, and a = 0 to 50, respectively).
R is H or Me;
W and Z _{are, CH 2 = CR-, CH 2} = CR-CH 2 -, - NHCH 2 -CR = CH 2, a -C≡CH, or W and Z are = CH ₂ (hence, It forms a double bond with the C atom to which W / Z is bonded.);
However, the W and Z groups in the monomer B'react with the amino X and Y groups in the monomer C'to form the C-NRa-CH ₂ -group. )
Represented by,
The binder according to claim 13. A binder as set forth請Motomeko 12 to 22, fillers, pigments, solvents, additives, hardeners and at least one fouling release coating composition comprising a catalyst. 請Motomeko 12 from a binder according to 22 antifouling coating composition comprising at least one marine antifouling agent. 23. The fouling release coating composition according to claim 23, which does not contain a biocide. Marine antifouling agents are N2-tert-butyl-N4-cyclopropyl-6-methylthio-1,3,5-triazine-2,4-diamine (cibutrin), 4,5-dichloro-2-n-octyl- 4-Isothiazolin-3-one (DCOIT ) , bis (1-hydroxy-2 (1H) -pyridinethionate-0, S)-(T-4) zinc (zinc pyridinethione; zinc pyrithione), bis (1) -Hydroxy-2 (1H) -pyridinethionate-0, S) -T-4) Copper (copper pyridinethione; copper pyrithione), zinc ethylene-1,2-bis-dithiocarbamate (zinc-ethylene-N-N) The antifouling coating composition according to claims 2 to 11 or 24 , which is selected from'-dithiocarbamate; Zinc), copper (I) oxide, metallic copper, copper thiocyanate, and copper sulfosocyanate. Comprising coating at least a portion of the prone body soiling with the coating composition of claim 2 to 11, 24 or 26, a method of protecting an object from fouling. 27. The method of claim 27, further comprising curing the coating composition. Coated object with a coating composition according to claims 1 to 11 or 23, 25. An object coated with the cured coating composition according to claims 1 to 11 or 23 to 25.