JP4994951B2 - Organopolysiloxane thioblock vinyl copolymer containing polyether-modified silicone, copolymer-containing composition thereof, antifouling coating composition, coating film thereof and antifouling method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organopolysiloxanethio-block vinyl copolymer that has a light environmental load, exerts little influence on the human body, exhibits excellent antifouling properties and persistency thereof and can form an antifouling film excellent in mechanical strength, and an antifouling coating composition comprising the copolymer. <P>SOLUTION: The organopolysiloxanethio-block vinyl copolymer comprises [A] a polymerizable group-containing polyether-modified silicone block, [B] a polyoxyalkylene group-containing vinyl copolymer block and [C] an organopolysiloxanethio-block and has a weight-average molecular weight (Mw) of 1,000-400,000 as measured by GPC. The antifouling coating composition comprises the copolymer. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to an organopolysiloxane thioblock vinyl copolymer suitably used as a resin for an antifouling paint, and an antifouling paint composition containing the copolymer, and more specifically, to environmental burdens and the human body. The present invention relates to an organopolysiloxane thioblock vinyl copolymer that can be suitably used as an antifouling paint and an antifouling paint composition containing the copolymer.

  Boat bottoms, fishing nets, seawater supply and drainage pipes, underwater structures, etc. are exposed to water for a long period of time, so that the surface of animals such as oysters, mussels and barnacles, plants such as laver (nori), or bacteria When various aquatic organisms such as these adhere and propagate, the appearance may be impaired and their functions may be impaired.

  In particular, when such aquatic organisms adhere to and propagate on the bottom of the ship, the surface roughness of the bottom of the ship increases, which may lead to a decrease in ship speed and an increase in fuel consumption. In addition, a great deal of labor and work time are required to remove such aquatic organisms from the ship bottom. In addition, when aquatic organisms adhere to and breed on fish nets such as aquaculture nets and stationary nets, serious problems such as oxygen deprivation of fish caught due to clogging of the nets may occur.

In addition, when aquatic organisms adhere to and breed on seawater supply / drainage pipes of thermal power, nuclear power plants, etc., the supply / distribution of cooling water may be hindered. Conventionally, in order to prevent such damage, as an antifouling paint having excellent antifouling properties, for example, a copolymer of tributyltin methacrylate and methyl methacrylate, cuprous oxide (Cu ₂ O, etc.) ) Was applied. The copolymer in the antifouling coating is hydrolyzed in seawater to give bistributyltin oxide (tributyltin ether, Bu ₃ Sn—O—SnBu ₃ : Bu is a butyl group) or tributyltin halide (Bu _3). Releases organotin compounds such as SnX: X is a halogen atom) and exhibits an antifouling effect, and the hydrolyzed copolymer itself becomes water-soluble and dissolves in seawater. Because it is a "type paint", the resin paint residue does not remain on the ship bottom coating surface, and an active surface can always be maintained.

  However, such organotin compounds are highly toxic, and there are concerns about marine pollution, the occurrence of malformed fish and malformed shellfish, the adverse effects on the ecosystem caused by the food chain, etc. Development of antifouling paints with good antifouling properties is required. In order to solve such problems, various studies and proposals have been made conventionally.

  For example, JP-B-7-57787, JP-A-5-51424, JP-A-5-279439, JP-A-8-134153, JP-A-8-259645, JP-A-11-21326, In JP-B-6-81824, JP-B-6-102772, and JP-A-7-305001, a graft copolymer comprising a (meth) acryl group-containing polyether-modified silicone and another polymerizable monomer is disclosed. Its use is disclosed for antifouling paints. However, the graft copolymer composed of the (meth) acryl group-containing polyether-modified silicone and other polymerizable monomers disclosed in these prior arts has insufficient long-term antifouling retention properties, and the resistance of the coating film. Physical properties such as cracking and strength were not sufficient.

JP-A-7-278467 and JP-A-11-106450 disclose (meta)
An antifouling paint is disclosed for a copolymer of acrylic group-containing polyether-modified silicone and methoxypolyethylene glycol monomethacrylate and its use. However, these antifouling coatings also have insufficient long-term antifouling retention properties and physical properties such as crack resistance and strength of the coating film are not sufficient.

JP 2002-327064 A (Patent Document 1) discloses an organopolysiloxane thioblock vinyl copolymer formed from a specific polyoxyalkylene group-containing vinyl copolymer block and a specific organopolysiloxane thioblock. By incorporating this into antifouling paints, the antifouling coating film has little impact on the environment and less impact on the human body, and has excellent antifouling properties and durability, and excellent mechanical strength. It is described that can be formed. However, further improvements have been desired in long-term antifouling retention properties and physical properties such as crack resistance and strength of the coating film.
JP 2002-327064 A

  The present invention seeks to solve the problems associated with the prior art as described above, and if incorporated in an antifouling paint, there is little impact on the environment and the human body, and the antifouling property and its Provided an organopolysiloxane thioblock vinyl copolymer for antifouling paints capable of forming an antifouling coating film having excellent durability and mechanical strength, and an antifouling paint composition containing the copolymer The purpose is to do.

The organopolysiloxane thioblock vinyl copolymer according to the present invention is
Has a lower Kipo Rieteru modified silicone block [A], the following polyoxyalkylene group-containing vinyl copolymer block [B], the following organopolysiloxane thio block [C],
Characterized by having a weight average molecular weight (Mw) measured by GPC of 1,000 to 400,000;
[A] Component unit (a1) derived from a modified silicone represented by the following formula [I] and / or Component unit (a2) derived from a modified silicone represented by the following formula [II]
A polyether-modified silicone block comprising:

[In Formula [I], each R ¹¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms,
R ¹² each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms,
R ¹³ and R ¹⁴ may be the same or different from each other and each independently represents an alkylene group having 2 to 4 carbon atoms,
R ¹⁵ represents a polymerizable unsaturated hydrocarbon group-containing group,
X represents a divalent hydrocarbon group or -YNHCOOZ-;
Y represents a diisocyanate compound residue;
Z represents a divalent hydrocarbon group.

  A, b, c, d, and e each represent a positive integer. ],

[In the formula [II], each R ²¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms,
R ²² each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms,
R ²³ and R ²⁴ may be the same or different from each other and each independently represents an alkylene group having 2 to 4 carbon atoms;
R ²⁵ represents a polymerizable unsaturated hydrocarbon group-containing group,
X, Y and Z are the same as X, Y and Z, respectively.

P, q, r, and s each represent a positive integer. ],
[B] A component derived from a polyoxyalkylene polymerizable unsaturated carboxylate represented by the following formula [III] and formed by forming an ester with a polymerizable unsaturated carboxylic acid at least at one end of a polyoxyalkylene compound unit Unit (b1) and / or Component unit (b2) derived from at least one non-crosslinked polymerizable unsaturated carboxylic acid or ester thereof other than the component unit (b1)
A polyoxyalkylene group-containing vinyl copolymer block having:
_{^{R 34 - [OR 31] m}} - [OR 32] n -OCOR 33 ··· [III]
[In the formula [III], R ³¹ and R ³² represent a divalent hydrocarbon group which may be the same or different from each other;
R ³³ represents a polymerizable unsaturated hydrocarbon group-containing group,
R ³⁴ represents a hydrogen atom, a monovalent hydrocarbon group that may have a polymerizable unsaturated bond, or a monobasic or dibasic organic carboxylic acid residue R that may have a polymerizable unsaturated bond. ³⁵ indicates CO-
R ³⁵ represents an organic group which may have a polymerizable unsaturated bond,
m and n each represent a positive integer. ],
[C] an organopolysiloxane thioblock comprising a component unit represented by the following formula [IV];

[In the formula [IV], R ⁴¹ represents a hydrocarbon group having 1 to 10 carbon atoms,
R ⁴² , R ⁴³ and R ⁴⁴ each independently represent R ⁴¹ or a divalent thioorganic group having 1 to 20 carbon atoms;
t and u each represent a positive integer. ].

  The polyoxyalkylene group-containing vinyl copolymer block [B] is further composed of a component unit (b3) derived from a crosslinkable polymerizable unsaturated monomer and / or other polymerizable unsaturated monomer. The component unit (b4) to be derived may be included.

The content of the above Kipo Rieteru modified silicone block [A] is 1 to 80 wt%, the content of the polyoxyalkylene group-containing vinyl copolymer block [B] is 5-98 wt%, the organopolysiloxane The content of the thioblock [C] is preferably 1 to 80% by weight (provided that the total of [A], [B] and [C] is 100% by weight).

The content of the above Kipo Rieteru modified silicone block [A] is from 5 to 50 wt%, the content of the polyoxyalkylene group-containing vinyl copolymer block [B] is 10 to 90 wt%, the organopolysiloxane The content of thioblock [C] is more preferably 5 to 50% by weight (provided that the total of [A], [B] and [C] is 100% by weight).

Upper Kipo Rieteru modified silicone block [A] is preferably a weight average molecular weight measured by GPC (Mw) is derived from a modified silicone is 300 to 100,000,
The organopolysiloxane thioblock [C] is preferably derived from a mercapto-modified polyorganosiloxane having a weight average molecular weight (Mw) measured by GPC of 300 to 100,000.

Polymerizable group on Kipo Rieteru modified silicone block [A] is preferably a (meth) acryloyl groups.
Upper Kipo Rieteru modified silicone block [A] is a polyoxyethylene group, preferably contains at least one group selected from the group consisting of polyoxypropylene groups and poly (oxyethylene-oxypropylene) group.

  The component unit (b2) derived from the non-crosslinked polymerizable unsaturated carboxylic acid or ester thereof is preferably a component unit derived from (meth) acrylic acid or ester thereof.

  The component unit (b1) derived from the polyoxyalkylene polymerizable unsaturated carboxylate is preferably a component unit derived from polyoxyalkylene (meth) acrylate.

  The crosslinkable group of the component unit (b3) derived from the above crosslinkable polymerizable unsaturated monomer is hydroxyl group, alkoxysilyl group, aryloxysilyl group, epoxy group, isocyanate group, carboxyl group, (meth) acryloxy It is preferably at least one of a group, a vinyl group, a silanol group, and an amino group.

  The component unit (b4) derived from the other polymerizable unsaturated monomers includes styrenes, vinyl esters, (meth) acrylamides, vinyl ethers, itaconic acid, maleic acid, fumaric acid, citraconic acid and the like. It is preferable that it is derived from any one or more of these derivatives and acrylonitrile.

The antifouling paint composition according to the present invention is characterized by containing the organopolysiloxane thioblock vinyl copolymer as a vehicle component.
The organopolysiloxane thioblock vinyl copolymer composition according to the present invention is characterized by containing the organopolysiloxane thioblock vinyl copolymer and a water repellent functional group-containing component.

The water repellent functional group-containing component is preferably silicone oils and / or paraffins.
Moreover, the antifouling coating composition according to the present invention may comprise the organopolysiloxane thioblock vinyl copolymer composition.

The antifouling paint composition according to the present invention may further contain an antifouling agent.
The antifouling coating film of the present invention is formed from the antifouling coating composition or the organopolysiloxane thioblock vinyl copolymer composition.

The base material of the present invention is characterized by being coated with the above antifouling coating film.
The underwater structure of the present invention is characterized in that the surface of the substrate is coated with the antifouling coating film.

The ship of the present invention is characterized in that the surface of the ship base is coated with the antifouling coating film.
The substrate antifouling method of the present invention is characterized in that the substrate surface is coated with the antifouling coating film.

  The organopolysiloxane thioblock vinyl copolymer according to the present invention, when used in, for example, an antifouling paint, has little impact on the environment and the human body, and is excellent in antifouling properties and its sustainability, and is mechanical. An antifouling coating film having excellent strength can be formed. In particular, the organopolysiloxane thioblock vinyl copolymer of the present invention exhibits the above characteristics even when silicone oils, paraffins, and the like are blended, and it can effectively suppress the weakening of the coating film. A film can be formed.

  Hereinafter, the organopolysiloxane thioblock vinyl copolymer that can be suitably used for an antifouling paint and the antifouling paint composition containing the copolymer will be described in detail.

[Organopolysiloxane thioblock vinyl copolymer]
Organopolysiloxane thio block vinyl copolymer according to the present invention includes a port Rieteru modified silicone block [A] as described below, the polyoxyalkylene group-containing vinyl copolymer block [B], an organopolysiloxane-thio block [ C].

  The weight average molecular weight (Mw) measured by GPC of such an organopolysiloxane thioblock vinyl copolymer is 1,000 to 400,000, preferably 3,000 to 200,000, and more preferably. Is 10,000 to 100,000. When the molecular weight is in such a range, the resulting copolymer has a viscosity suitable for handling at a concentration suitable as a solution or antifouling coating composition, and the antifouling coating composition containing the copolymer is: The viscosity becomes suitable for coating, and the resulting coating film (especially antifouling coating film) has an appropriate strength and tends to be excellent in antifouling durability.

<Polyether-modified silicone block [A]>
The organopolysiloxane thioblock vinyl copolymer of the present invention comprises a component unit (a1) derived from a polyether-modified silicone represented by the following formula [I] and / or a polysiloxane represented by the following formula [II]. and a constituent unit derived from the polyether-modified silicone (a2) Tona Lupo Rieteru modified silicone block [a].

In the above formula [I],
R ¹¹ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of R ¹¹ include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an aryl group such as a phenyl group and a tolyl group; Examples include aralkyl groups such as benzyl group and 2-phenylethyl group; halogenated alkyl groups such as 3,3,3-trifluoropropyl group and 3-chloropropyl group. Among these, a methyl group, an ethyl group, a phenyl group, a vinyl group, and a 2-phenylethyl group are preferable, a methyl group is particularly preferable, and all R ¹¹ are particularly preferably a methyl group.

R < ¹² > shows a C1-C6 bivalent hydrocarbon group each independently. As R ¹² , for example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₂ — and other divalent hydrocarbon groups can be mentioned. Among these, —CH ₂ CH ₂ —, —
CH ₂ CH ₂ CH ₂ — is preferable, and —CH ₂ CH ₂ CH ₂ — is particularly preferable.

R ¹³ and R ¹⁴ may be the same or different from each other, and each independently represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group include —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH (CH ₃ ) CH ₂ —, —CH ₂ CH _2.
Examples include alkylene groups such as CH ₂ CH ₂ —, and among these, —CH ₂ CH ₂ —, —CH ₂
CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, and —CH (CH ₃ ) CH ₂ — are preferable, and —CH ₂ CH ₂ — is particularly preferable.

Therefore, (R ¹³ —O) _a (R ¹⁴ —O) _b is preferably a polyoxyethylene group, a polyoxypropylene group, a polyether group containing both, and a poly (oxyethyleneoxypropylene) group.

The number a of repeating units (R ¹³ —O) and the number b of repeating units (R ¹⁴ —O) are each independently 1 to 30, preferably 2 to 20, particularly preferably 3 to 15. Is an integer.

In addition, the (R ¹³ —O) unit and the (R ¹⁴ —O) unit that are repeated may be the same as or different from each other. Therefore, for example, as the above (R ¹³ —O) unit and (R ¹⁴ —O) unit, (CH ₂ CH ₂ —O) unit, (CH ₂ CH ₂ CH ₂ —O) unit or (C
H ₂ CH (CH ₃ ) —O) units may be alternately arranged and bonded one by one, each forming an arbitrary number of blocks, and the total number of each repeating unit is a , B may be used.

R ¹⁵ is a polymerizable unsaturated hydrocarbon group-containing group, and examples of R ¹⁵ include a vinyl group CH _{2
= CH-, CH 2 = C (} CH 3) -, CH 3 -CH = CH-, CH 3 -CH = C (CH 3) -
, HOCOCH═CH—, CH ₃ OCOCH═CH—, etc., and the total number of carbon atoms is 2 to 15, preferably 2 to 10, and a polymerizable unsaturated hydrocarbon group-containing group which may have a substituent. Can be mentioned.

Accordingly, —OCOR ¹⁵ (that is, R ¹⁵ COO—) represents a polymerizable unsaturated carboxylic acid residue, and examples of —OCOR ¹⁵ (R ¹⁵ COO—) include acryloyloxy group (CH ₂ ═CHCOO—), In addition to a methacryloyloxy group (CH ₂ ═C (CH ₃ ) COO—), 2
A group such as a maleoyloxy group (HOOCCH = CHCOO-, cis), a fumaroyloxy group (HOOCCH = CHCOO-, trans) derived from a basic polymerizable unsaturated carboxylic acid, and an ester thereof, 3 to 16, preferably 3 to 11, and a polymerizable unsaturated carboxylic acid residue (polymerizable unsaturated group-containing carbonyloxy group) which may have a substituent (eg, —COOH). .

X represents a divalent hydrocarbon group or —YNHCOOZ—, Y represents a diisocyanate compound residue, and Z represents a divalent hydrocarbon group.
Examples of the diisocyanate compound include aliphatic, aromatic, alicyclic isocyanate, and both-end reactive isocyanate oligomers. For example, diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), p-phenylene diisocyanate, trans-1,4-cyclohexane diisocyanate (CHDI), 1,3-bis- (isocyanatomethyl-benzene, 4,4'-dicyclohexylmethane diisocyanate (H12MDI ), 1,3-bis- (isocyanatomethyl) -cyclohexane (H6XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), meta-tetramethylxylene diisocyanate or para-tetramethylxylene Isocyanate (m-TMXDI, p-TMXDI), lysine diisocyanate (LDI), 2,2,4-trimethylhexamethylene diisocyanate, and the like. Among these, tolylene diisocyanate (TDI), Isophorone diisocyanate (IPDI) is preferred.

Moreover, the carbon atom number of X is 1-8 normally, Preferably it is 1-4, and the carbon atom number of Z is 1-12 normally, Preferably it is 2-6.
C is a repeating unit

The above-mentioned d is a repeating unit.

Indicates the total number (positive number), and e is a repeating unit.

The number of repeating units may be combined in an arbitrary order, and the total number of repeating units may be c, d, and e, respectively. For example, each repeating unit may be alternately arranged and connected one by one, each forming an arbitrary number of blocks, and the total number of each repeating unit being c, d, and e, respectively. May be.

In the above formula [II],
R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are the same as R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ , respectively.

The number of repeating units p of (R ²³ —O) and the number of repeating units q of (R ²⁴ —O) are each an integer of 1 to 30, preferably 2 to 20, particularly preferably 3 to 15. .
In addition, the (R ²³ —O) unit and the (R ²⁴ —O) unit that are repeated may be the same as or different from each other. Therefore, for example, as the above (R ¹³ —O) unit and (R ²⁴ —O) unit, (CH ₂ CH ₂ —O) unit, (CH ₂ CH ₂ CH ₂ —O) unit, (CH ₂ CH (CH) ₃ ) -O) units or (CH (CH ₃ ) CH ₂ -O) units may be alternately arranged and bonded one by one, each forming an arbitrary number of blocks, The total number of repeating units may be p or q.

  The above r is a repeating unit

The total number (positive number) of

Indicates the total number (positive number).
Upper Kipo Rieteru modified silicone block [A] or corresponding to the aforementioned formula polyether-modified silicone and the above formula is represented by [I] [II] in a weight average molecular weight measured by GPC of the polyether-modified silicone represented ( Mw) is preferably 300 to 100,000.

<Manufacturing method>
The compound represented by the above formula [I] is, for example,

A compound represented by
OCNXOCOR ¹⁵ ... [b]
[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , a, b, c, d and e are the same as described above. ]
It can manufacture by making the compound represented by these react.

  The compound represented by the above formula [II] is, for example,

A compound represented by
OCNXOCOR ²⁵ ... [b]
[R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , p, q, r and s are the same as described above. ]
It can manufacture by making the compound represented by these react.

  As the modified silicone represented by the above formula [Ia], “FZ-2191 (trade name)” (manufactured by Toray Dow Co., Ltd.), “SH-3771 (trade name)” (Toray Dow ( Co., Ltd.), “KF-353A (trade name)” (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Moreover, as modified silicone represented by the said formula [II-a], if it is a commercial item, "SF-8427 (brand name)" (made by Toray Dow Co., Ltd.) etc. will be mentioned.

  As the compound represented by the above formula [b], when X is a divalent hydrocarbon group, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxymethyl isocyanate, 2-acryloyloxymethyl isocyanate, Examples thereof include 2-methacryloyloxybutyl isocyanate and 2-acryloyloxybutyl isocyanate. Among these, 2-methacryloyloxyethyl isocyanate can be preferably used.

Moreover, if it is a commercial item, "Karenz MOI (trademark)" (made by Showa Denko KK) "Karenz AOI (trademark)" (made by Showa Denko KK) etc. will be mentioned, for example.
When X is -YNHCOOZ-, Y is a diisocyanate compound residue, and Z is a divalent hydrocarbon group, the reaction product of the diisocyanate compound and a hydroxyl group-containing (meth) acrylic ester is Can be mentioned. As the hydroxyl group-containing (meth) acrylic acid ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxy And hexyl (meth) acrylate. The reaction between the diisocyanate compound and the hydroxyl group-containing (meth) acrylic acid ester is compounded such that the equivalent ratio of isocyanate group / hydroxyl group is 1.0 / 0.5 to 1.0 / 0.7, It is preferable to react. The reaction temperature is usually 0 to 150 ° C., preferably 40 to 100 ° C. In the reaction, a urethane reaction catalyst such as dibutyltin dilaurate may be used. In the reaction, a polymerization inhibitor such as p-methoxyquinone or hydroquinone may be present. In the reaction, an organic solvent may be used, and examples of the organic solvent include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, xylene, cellosolve acetate and the like.

  In the reaction of the compound represented by the above formula [Ia] with the compound represented by the above formula [b], depending on the molecular weight and the number of hydroxyl groups of [Ia], these compounds are converted into isocyanate groups / It is preferable to mix and react such that the equivalent ratio of hydroxyl groups is 0.01 / 1.0 to 0.5 / 1.0. In particular, the compound represented by [Ia] and the compound represented by [b] are preferably mixed and reacted so as to have the same mole.

  Similarly, in the reaction of the compound represented by the formula [II-a] and the compound represented by the formula [b], an equivalent ratio of isocyanate group / hydroxyl group is 0.4 / 1.0 to 0. It is preferable to mix and react so that the ratio is 6 / 1.0. In particular, the compound represented by [II-a] and the compound represented by [b] are preferably blended so as to have the same mole and reacted.

  In addition, this reaction can be performed at the same reaction temperature as the reaction between the diisocyanate compound and the hydroxyl group-containing (meth) acrylic acid ester, and the same urethane reaction catalyst as the reaction may be used. A polymerization inhibitor may be present, and an organic solvent similar to the reaction may be used.

  Here, if the amount of the compound represented by the formula [b] is small, a polyether-modified silicone containing no polymerizable group is generated, and the coating strength is reduced due to the presence of the polyether-modified silicone that does not contribute to the reaction. The organopolysiloxane thioblock vinyl copolymer tends to cause cloudiness and separation, and if the amount of the compound represented by [b] is too large, gelation occurs during the copolymerization of the organopolysiloxane thioblock vinyl. It tends to happen.

<Polyoxyalkylene group-containing vinyl copolymer block [B]>
The polyoxyalkylene group-containing vinyl copolymer block [B] is:
(B1) represented by the following formula [III], polyoxyalkylene compound at least its one end with by forming a heavy polymerizable unsaturated carboxylic acid ester polyoxyalkylene polymerizable unsaturated carboxylate (hereinafter "monomer ( b1) ”))) and / or (b2) at least other than the component (b1) described above (hereinafter also referred to as“ polyoxyalkylene polymerizable unsaturated carboxylate component unit (b1) ”). Component unit derived from one kind of non-crosslinked polymerizable unsaturated carboxylic acid or ester thereof (hereinafter also referred to as “monomer (b2)”) (hereinafter “non-crosslinked polymerizable unsaturated carboxylic acid component unit (b2)” ) "), And
(B3) A component unit derived from a crosslinkable polymerizable unsaturated monomer (hereinafter also referred to as “monomer (b3)”) (hereinafter “crosslinked polymerizable unsaturated monomer component unit ( b3) "),
(B4) A component unit derived from another polymerizable unsaturated monomer (hereinafter also referred to as “monomer (b4)”) (hereinafter “other polymerizable unsaturated monomer component unit ( b4) ".)).

First, the polyoxyalkylene polymerizable unsaturated carboxylate component unit (b1) will be described.
<Polyoxyalkylene polymerizable unsaturated carboxylate component unit (b1)>
The polyoxyalkylene polymerizable unsaturated carboxylate component unit (b1) is a component unit derived from the polyoxyalkylene polymerizable unsaturated carboxylate [III] represented by the following formula [III].

_{^{R 34 - [OR 31] m}} - [OR 32] n -OCOR 33 ··· [III]
In the formula [III], R ³¹ and R ³² represent a divalent hydrocarbon group which may be the same or different from each other, and examples thereof include aliphatic, alicyclic, and aromatic groups. Specifically, for example, a methylene group, an ethylene group, a propylene group (trimethylene: — (CH ₂ ) ₃ —, methyl dimethylene: —CH ₂ CH (CH ₃ ) —), a butylene group (tetramethylene), etc. And a polymethylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.

R ³³ represents a polymerizable unsaturated hydrocarbon group-containing group, such as a vinyl group (CH ₂ ═CH—).
_{, CH 2 = C (CH 3} ) -, CH 3 -CH = CH-, CH 3 -CH = C (CH 3) -, HOC
OCH═CH—, CH ₃ OCOCH═CH—, etc., having a total carbon number of 2-15, preferably 2
10 is an unsaturated hydrocarbon group-containing group which may have a substituent.

Accordingly, —OCOR ³³ (ie, R ³³ COO—) represents a polymerizable unsaturated carboxylic acid residue, and —OCOR ³³ (ie, R ³³ COO—) includes, for example, a (meth) acryloyloxy group [CH ₂ = C (H or CH ₃ ) COO-], maleoyloxy groups (HOOCCH = CHCOO-, cis) derived from dibasic polymerizable unsaturated carboxylic acids, fumaroyloxy groups (HOOCCH = CHCOO-, trans A polymerizable unsaturated carboxylic acid having a total carbon number of 3 to 16, preferably 3 to 11, and optionally having a substituent (e.g., -COOH). And a residue (polymerizable unsaturated group-containing carbonyloxy group).

R ³⁴ represents a hydrogen atom (A), a monovalent hydrocarbon group (B) optionally having a polymerizable unsaturated bond, or an organic carboxylic acid residue optionally having a polymerizable unsaturated bond “R ³⁵ CO- (R ³⁵
Represents an organic group which may contain a polymerizable unsaturated bond. ) "(C). This organic carboxylic acid residue (c) may be monobasic or dibasic.

When R ³⁴ is a monovalent hydrocarbon group (b) optionally having a polymerizable unsaturated bond, examples of such hydrocarbon group (b) include the same groups as R ³³ described above. CH ₂ = CH
_{-, CH 2 = C (CH} 3) -, CH 3 -CH = CH-, CH 3 -CH = C (CH 3) - in addition to _{such, CH 3 -, C 2 H} 5 -, C 3 H 7 -, C ₄ H _9- and the like.
An alkyl group having 5 carbon atoms; an aryl group having 6 to 20 carbon atoms which may have a substituent; CH ₃ CO—
, C ₂ H ₅ CO—, C ₃ H ₇ CO—, C ₄ H ₉ CO— and the like, such as an alkylcarbonyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Among these, R ³⁴ is preferably a hydrogen atom (I) or the above alkyl group.

The alkyl group contained in the alkyl group or the alkylcarbonyl group may be linear, branched, or alicyclic. In said formula [III], m and n show a positive number, Preferably, they are numbers of 1-50, respectively. As the polyoxyalkylene polymerizable unsaturated carboxylate [III] from which such a polyoxyalkylene polymerizable unsaturated carboxylate component unit (b1) can be derived, paragraph [0009] of JP-A-9-216922 is disclosed.
Can be used. Specifically, for example,
Polyethylene glycol monomethacrylate (eg: Bremer PE series, PE-90, PE-200, PE-350 manufactured by NOF Corporation),
Methoxypolyethylene glycol monomethacrylate (Example: Bremer PME series, PME-100, PME-200, PME-400 manufactured by NOF Corporation; NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd., M-20G, M-40G, M-90G, M-230G),
Polypropylene glycol monomethacrylate (Example: Bremer PP series, PP-1000, PP-500, PP-800 manufactured by NOF Corporation),
Polyethylene glycol Polypropylene glycol monomethacrylate (Example: Bremer PEP series, 70PEP-370B manufactured by NOF Corporation),
Polyethylene glycol polytetramethylene glycol monomethacrylate (eg, Bremer 55PET-800 manufactured by NOF Corporation),
Polypropylene glycol polytetramethylene glycol monomethacrylate (eg, Bremer NKH-5050 manufactured by NOF Corporation),
Polypropylene glycol monoacrylate (eg, Bremer AP-400 manufactured by NOF Corporation),
Polyethylene glycol monoacrylate (eg, Bremer AE-350 manufactured by NOF Corporation),
Methoxypolyethylene glycol monoacrylate: [H ₃ C— (OC ₂ H ₄ ) _{m + n} —OC
O (CH) = CH ₂ ],
Ethoxy polyethylene glycol _{monomethacrylate: [H 5 C 2 - (} OC 2 H 4) m + n -OCOC (CH 3) = CH 2],
Methylcarboxypolyethylene glycol monomethacrylate: [H ₃ C—CO— (OC ₂ H ₄ ) _{m + n} —OCOC (CH ₃ ) ═CH ₂ ],
Methyl carboxy polypropylene glycol monomethacrylate: [H ₃ C—CO— (O
_{C 3 H 6) m + n} -OCORC (CH 3) = CH 2],
Methoxy polyethylene glycol polypropylene glycol _{monomethacrylate: [H 3 C- (OC 2} H 4) m (OC 3 H 6) n -OCORC (CH 3) = CH 2],
Carboxymethylenecarboxypolyethylene glycol monomethacrylate: [HOCO—CH ₂ —CO (OC ₂ H ₄ ) _{m + n} —OCOC (CH ₃ ) ═CH ₂ ],
Hydroxy Murray oil polyethylene glycol _{monomethacrylate: [HOOCCH = CHCO (OC 2} H 4) m + n -OCOC (CH 3) = CH 2],
Polyethylene glycol _{dimethacrylate: [CH 2 = CHCO- (OC} 2 H 4) m + n -O
COC (CH ₃ ) = CH ₂ ],
Polyethylene glycol _{dimethacrylate: [CH 2 = C (CH} 3) CO- (OC 2 H 4) m + n -OCOC (CH 3) = CH 2],
Phenoxy polyethylene glycol monomethacrylate:

Etc. These are used alone or in combination of two or more. Of these polyoxyalkylene polymerizable unsaturated carboxylates [III], polyoxyalkylene (meth) acrylates (oxyalkylene group having 1 to 10 carbon atoms) are preferred, and methoxypolyethylene glycol mono (meta) ) Acrylate (ethylene glycol repeat number: 2 to 100) is desirable.

<Non-crosslinked type polymerizable unsaturated carboxylic acid component unit (b2)>
The non-crosslinked polymerizable unsaturated carboxylic acid component unit (b2) is “at least one non-crosslinked type (also referred to as non-crosslinkable) other than the component polyoxyalkylene polymerizable unsaturated carboxylate component unit (b1)”. )) Polymerizable unsaturated carboxylic acid or ester thereof.

Examples of such a (non-crosslinked type) polymerizable unsaturated carboxylic acid or ester thereof include Japanese Patent No. 2939309, page 13, right column, rear column to page 14, left column, upper column, or JP-A-9-100445, page 3. The polymerizable vinyl monomer described in the left column to the right column, paragraph [0007] can be used, and specifically, for example,
Α, β-unsaturated carboxylic acids and acid anhydrides such as (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, citraconic acid, maleic anhydride;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl ( (Meth) acrylate, octadecyl (meth) acrylate, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate The number of carbon atoms, such bets is about 1 to 30, aliphatic, (meth) acrylic acid esters of alicyclic or aromatic;
Amino group-containing unsaturated carboxylic acid esters such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate;
Silicon-containing unsaturated carboxylic acid esters such as (meth) acryloxypropyl polydimethylsiloxane;
Examples include fluorine-containing unsaturated carboxylic acid esters such as 2,2,2-trifluoroethyl (meth) acrylate and 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate.

  These polymerizable unsaturated carboxylic acids, acid anhydrides and polymerizable unsaturated carboxylic acid esters can be used singly or in combination of two or more. Of these polymerizable unsaturated carboxylic acids, acid anhydrides and polymerizable unsaturated carboxylic acid esters, the above (meth) acrylic acid and its esters are preferable, and further, aliphatics and alicyclics having 1 to 30 carbon atoms. The above-mentioned (meth) acrylic acid and alkyl esters thereof are desirable.

<Crosslinked polymerizable unsaturated monomer component unit (b3)>
Examples of the crosslinkable polymerizable unsaturated monomer component unit (b3) include component units derived from a crosslinkable polymerizable unsaturated monomer other than the above (b1) and (b2).

Examples of the crosslinkable polymerizable unsaturated monomer capable of deriving the polymerizable unsaturated monomer component unit (b3) having such a crosslinkable group (also referred to as a crosslinkable group) include, for example, a crosslink used if necessary. As polymerizable unsaturated monomers having an OH group capable of reacting with the agent, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, (poly) caprolactone (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc.
In addition, self-crosslinkable hydrolyzable silyl group-containing polymerizable unsaturated monomers include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth). Acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethoxyethoxysilane, vinyltriacetoxysilane, p-trimethoxysilylstyrene, p-triethoxysilylstyrene , P-trimethoxysilyl-α-methylstyrene, p-triethoxysilyl-α-methylstyrene, vinyltrimethoxysilane, vinyltriethoxysilane, N-β (N-vinylbenzylaminoethyl-γ-aminopropyl) tri Methoxysilane, hydrochloride, etc.
Polymerizable unsaturated monomers having an epoxy group capable of reacting with a crosslinking agent used as necessary include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl ( (Meth) acrylate, etc.
(Meth) acryloyl isocyanate, 2- (meth) acryloxyethyl isocyanate, etc. are mentioned as polymerizable unsaturated monomers having an isocyanate group capable of self-crosslinking or reacting with a crosslinking agent used as necessary.
Examples of the polymerizable unsaturated monomer having a carboxyl group capable of reacting with a crosslinking agent used as necessary include (meth) acrylic acid, maleic acid and derivatives thereof, itaconic acid and derivatives thereof, and the like.

  The component unit (b3) derived from the above-mentioned crosslinkable polymerizable unsaturated monomer is a component unit (b3) having a (meth) acryloxy group or vinyl group which is a crosslinkable group by radical polymerization or the like, if necessary. To the component unit (b3) having a silanol group or an amino group, which is another cross-linking system.

  Of these “crosslinkable polymerizable unsaturated monomers”, the organopolysiloxane thioblock vinyl copolymer can be obtained from the viewpoint of film-forming properties, coating strength, heat resistance, oil resistance, and the like. In a coating film obtained from a coating material containing a polymer, it is desirable that the copolymer forms a crosslinked structure. “Crosslinkable polymerizable unsaturated monomer” includes hydroxyl group, alkoxysilyl group, aryloxysilyl group, epoxy group, isocyanate group, carboxyl group, (meth) acryloxy group, vinyl group, silanol group, amino group, etc. A crosslinkable polymerizable unsaturated monomer having at least one functional group, preferably a hydroxy group, an isocyanate group, an epoxy group, or an alkoxysilyl group. It is desirable.

These crosslinkable polymerizable unsaturated monomers include 2-hydroxyethyl (meth) acrylate, 3 (or 2) -hydroxypropyl (meth) acrylate, 4 (or 2) -hydroxybutyl (meth) acrylate, γ -(Meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, glycidyl ( It is particularly desirable to use (meth) acrylates.

These “crosslinked polymerizable unsaturated monomers” can be used singly or in combination of two or more.
<Other polymerizable unsaturated monomer component unit (b4)>
Examples of the other polymerizable unsaturated monomer component unit (b4) include component units derived from polymerizable unsaturated monomers used as necessary other than the above (b1), (b2), and (b3). It is done.

The polymerizable unsaturated monomer capable of deriving such a component unit (b4) is any known monomer as long as it is a radical polymerizable unsaturated monomer capable of forming a vinyl copolymer block component. For example, styrenes such as styrene and α-methylstyrene;
Vinyl esters such as vinyl acetate and vinyl propionate;
Acrylamides such as N, N-dimethylacrylamide and dimethylaminoethylacrylamide;
Vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether;
Dibasic polymerizable monomers such as itaconic acid, maleic acid, fumaric acid, citraconic acid and esters thereof;
Examples include acrylonitrile.

These “other polymerizable unsaturated monomers” can be used alone or in combination of two or more as required. In the present invention, in the polyoxyalkylene group-containing vinyl copolymer block [B] (100% by weight),
The polyoxyalkylene polymerizable unsaturated carboxylate component unit (b1) is usually 0.1 to 40% by weight, preferably 0.5 to 30% by weight, particularly preferably 1.0 to 20% by weight,
The polymerizable unsaturated carboxylic acid component unit (b2) is usually contained in an amount of 60 to 99.9% by weight, preferably 70 to 99.5% by weight, particularly preferably 80 to 99.0% by weight. It is desirable that

In addition, the crosslinkable polymerizable unsaturated monomer component unit (b3) is usually in an amount of 0 to 39% by weight, preferably 0 to 29% by weight, particularly preferably 0 to 19% by weight,
The other polymerizable unsaturated monomer component unit (b4) is usually contained in an amount of 0 to 39% by weight, preferably 0 to 29% by weight, particularly preferably 0 to 19% by weight. .

  When the component units (b1), (b2), (b3), and (b4) are contained in such a quantity in the polyoxyalkylene group-containing vinyl copolymer block [B], the resulting organopolysiloxane Siloxane thioblock vinyl copolymers (also referred to as “silicone block vinyl copolymers”) have an appropriate film-forming property, tend to have good coating strength and excellent antifouling properties.

  The glass transition temperature (Tg) of the polyoxyalkylene group-containing vinyl copolymer block [B] or the corresponding polyoxyalkylene group-containing vinyl copolymer is usually −75 ° C. or higher, preferably −30 ° C. or higher. It is desirable from the viewpoint of film forming property.

  The organopolysiloxane thioblock vinyl copolymer of the present invention contains (meth) acryl group-containing polyether-modified silicone block [A] in an amount of 1 to 80% by weight, preferably 5 to 50% by weight, and contains a polyoxyalkylene group. The vinyl copolymer block [B] is present in an amount of 5 to 98% by weight, preferably 10 to 90% by weight, and the organopolysiloxane thioblock [C] is present in an amount of 1 to 80% by weight, preferably 5 to 50% by weight. It is desirable that

When each block [A], [B], and [C] is contained in the organopolysiloxane thioblock vinyl copolymer in such an amount, the organopolysiloxane thioblock vinyl copolymer is difficult to adhere. There is a tendency that the surface is formed and the antifouling property is improved. In the polyoxyalkylene group-containing vinyl copolymer block [B], a polymerizable unsaturated bond (carbon-carbon double bond) in the monomer (polyoxyalkylene polymerizable unsaturated carboxylate [III]). Is a component unit (b1) formed by cleavage of a polymerizable unsaturated bond contained in the corresponding monomer, and a component unit (b3) used as necessary. It is considered that and the component unit (b4) are connected at random or arranged in blocks to form a copolymer block.

<Organopolysiloxane thioblock [C]>
The organopolysiloxane thioblock [C] constituting the organopolysiloxane thioblock vinyl copolymer of the present invention is represented by the following formula [IV].
[C] General formula [IV]:

In the formula [IV], each of the plurality of R ⁴¹ independently represents a hydrocarbon group having 1 to 10 carbon atoms, and examples of R ⁴¹ include a methyl group, an ethyl group, a propyl group, and an isobutyl group. An alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, particularly preferably 1 to 3 carbon atoms, a phenyl group, 2-
A phenylethyl group, a fluoroalkyl group, etc. are mentioned, Preferably the said alkyl group, especially a methyl group are desirable.

R ⁴² , R ⁴³ and R ⁴⁴ each independently represent R ⁴¹ or a divalent organic group having 1 to 20 carbon atoms, preferably a divalent thioorganic group having the carbon number (eg, thiohydrocarbon). Group) or the same group as R ⁴¹ described above, more preferably the divalent thioorganic group.

The divalent thio organic group is represented by the formula: “—SX—” (X: a divalent organic group which may have a substituent). As the thioorganic group,
As shown in Japanese Patent No. 2863562, page 3, thiomethylene group (-S-CH ₂
-), Chiojimechiren group _{(-S- (CH 2) 2 -} ), thio propylene _{"-S-CH 2 CH 2 CH 2} -, - SCHCH 3 CH 2 -, - SCH 2 CHCH 3 - ", thio dimethylmethylene Group
_{-S-C (CH 3) 2} - ", Chiobuchiren group" _{-S-CH 2 CH (CH 3} ) CH 2 - ", thio dimethylethylene group" _{-S-CH 2 C (CH 3} ) 2 - ", thio Octamethylene group “—S— (CH ₂ ) ₈
A thiohydrocarbon group having a branched divalent hydrocarbon group having 1 to 10 carbon atoms, which may have a branch, such as “-” and the like;
Thio having an aromatic divalent hydrocarbon group such as a thiophenylene group “—S—C ₆ H ₄ —”, a thiophenylene ethylene group “—S—C ₆ H ₄ — (CH ₂ ) ₂ —”, etc. A hydrocarbon group;
Moreover, it has a structure obtained by adding HS-CH ₂ COOH and HS-CH ₂ CH ₂ COOH to a polydimethylsiloxane compound having an epoxy group at the end as described in JP-A-9-100445. A thioorganic group having a derived divalent organic group;
Etc.

Among these thioorganic groups “—SX—”, a thiohydrocarbon group having a chain divalent hydrocarbon group (X) having 1 to 5 carbon atoms such as a thiotrimethylene group is preferable.
The t represents the total number (positive number) of the repeating unit [Si (R ⁴¹ ) ₂ —O], and u is similarly the total number of the repeating unit [Si (R ⁴¹ ) (R ⁴⁴ ) —O]. (Positive number), and each repeating unit [Si (R ⁴¹ ) ₂ —O] and [Si (R ⁴¹ ) (R ⁴⁴ ) —O] are bonded in any order to form each repeating unit. The total number may be t and u, respectively. For example, the repeating units may be alternately arranged and connected one by one, each may be arranged in an arbitrary number of blocks, and the total number of repeating units may be t and u, respectively. Good.

Such organopolysiloxane thioblock [C] includes the following four types (1) to (4) depending on the types of R ⁴² , R ⁴³ and R ^{44 in} the formula [IV]. (These formulas [IV-1] to [IV-
4a], R ⁴⁵ represents a divalent organic group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. R ⁴¹ is the same as that in formula [IV]. )
(1) In the formula [IV], one end group R ⁴² or R ⁴³ of the organopolysiloxane is a divalent thioorganic group, and the other, R ⁴³ and R ⁴⁴ are the same as R ⁴¹ The base of (single-end type):

  Examples of the mercapto-modified polyorganosiloxane [IV-1a] from which such an organopolysiloxane thioblock [IV-1] can be derived include the following.

(In the formulas [IV-1] and [IV-1a], R ⁴⁵ represents a propylene group “—CH (CH ₃ ) CH ₂ —” or trimethylene group “— (CH ₂ ) ₃ —”, R ⁴¹ represents a methyl group, (A phenyl group and a fluoroalkyl group are t + u = 2 to 1,500 integers.)
More specifically, as such mercapto-modified polyorganosiloxane [IV-1a], α-mercaptopropyl polydimethylsiloxane, epoxy group-containing polydimethylsiloxane (product names: “Silaplane FM-0511, FM-0521, FM -0525 ", made by Chisso Corporation)
Examples include mercaptopropionic acid adducts.

(2) In the formula [IV], R ⁴² and R ⁴³ are both divalent thiohydrocarbon groups, and R ⁴⁴ is the same group as R ⁴¹ (both terminal types):

  Examples of the mercapto-modified polyorganosiloxane [IV-2a] from which such an organopolysiloxane thioblock [IV-2] can be derived include the following.

(In the formulas [IV-2] and [IV-2a], R ⁴⁵ represents a propylene group “—CH (CH ₃ ) CH ₂ —” or trimethylene group “— (CH ₂ ) ₃ —”, R ⁴¹ represents a methyl group, A phenyl group, a fluoroalkyl group, and an integer of t + u = 2 to 1500.) Such mercapto-modified polyorganosiloxane [IV
-2a], more specifically, “X-22-167B” manufactured by Shin-Etsu Chemical Co., Ltd. and the like.

(3) In the formula [IV], both R ⁴² and R ⁴³ are the same groups as R ^41, and at least one (u-w) of plural (u) R ⁴⁴ is 2 The remaining R ⁴⁴ (w) is the same group as R ⁴¹ , or all of R ⁴⁴ (w = 0, u) are divalent. Those having a thiohydrocarbon group (side chain type):

  Examples of mercapto-modified polyorganosiloxane [IV-3a] from which such organopolysiloxane thioblock [IV-3] can be derived include the following.

(In the formulas [IV-3] and [IV-3a], R ⁴⁵ represents a propylene group “—CH (CH ₃ ) CH ₂ —” or trimethylene group “— (CH ₂ ) ₃ —”, and R ⁴¹ represents a methyl group. T = 1 to 1500, u = 1 to 100, 0 ≦ w ≦ u (w: integer).) As such mercapto-modified polyorganosiloxane [IV-3a], more specifically, Product name “KF-200” manufactured by Shin-Etsu Chemical Co., Ltd.
1, KF-2004, KP-358 "and the like.

(4) In the formula [IV], both R ⁴² and R ⁴³ are divalent thiohydrocarbon groups, and at least one (u-w) of R ⁴⁴ is a divalent thiohydrocarbon. And the remainder (w) of R ⁴⁴ is the same group as R ⁴¹ , or all of R ⁴⁴ (w = 0, u) is a divalent thiohydrocarbon group. Things (both side chain type):

(In these formulas [IV-1] to [IV-4], R ⁴⁵ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. R ⁴¹ in formula [IV] Same as the thing.)
Examples of the mercapto-modified polyorganosiloxane [IV-4a] from which such an organopolysiloxane thioblock [IV-4] can be derived include the following.

(In the formulas [IV-4] and [IV-4a], R ⁴⁵ represents a propylene group “—CH (CH ₃ ) CH ₂ —” or trimethylene group “— (CH ₂ ) ₃ —”, and R ⁴¹ represents a methyl group. T = 1 to 1500, u = 1 to 100, 0 ≦ w ≦ u (w: integer).)
In the present specification, the mercapto-modified polyorganosiloxane [IV-1a], the mercapto-modified polyorganosiloxane [IV-2a], the mercapto-modified polyorganosiloxane [IV-3a], and the mercapto-modified polyorganosiloxane [IV −4a] is also collectively referred to as “mercapto-modified polyorganosiloxane [IV-a]”.

The number of the thioether group “—S—” in the various organopolysiloxane thioblocks [C] or the mercapto group (—SH group) in the corresponding mercapto-modified polyorganosiloxane is, for example, JP-A-9-216922. No. (Showa Denko Co., Ltd.)
) As shown also in the column [0015] on page 5, it is generally 1.0 to 100, preferably 1.0 to 50, more preferably 1.0 to 1 block (or one molecule) on average. 30 is desirable.

  Moreover, the weight average molecular weight (Mw) measured by GPC of the said organopolysiloxane thioblock [C] or corresponding mercapto modified polyorganosiloxane is 300-100,000, Preferably it is 500-50,000. desirable.

Note that if the block including the port Rieteru modified silicone block [A] and the polyoxyalkylene group-containing vinyl copolymer block [B] represents a "block [AB]",
The organopolysiloxane thioblock [C] in the organopolysiloxane thioblock vinyl copolymer of the present invention is derived from a mercapto-modified polyorganosiloxane [IV-1a] having one mercapto group at the molecular fragment end of the polyorganosiloxane. In the case of the above-mentioned one-end type [IV-1], the structure of the organopolysiloxane thioblock vinyl copolymer of the present invention is an organopolysiloxane thioblock at one or both ends of the block [AB]. A block copolymer ([AB] / [C] type or [C] / [AB] / [C] type) with [C] added (end-capped),
In addition, when the organopolysiloxane thioblock [C] is the above-mentioned both terminal types [IV-2], a block copolymer in which the block [AB] is added to both ends of the organopolysiloxane thioblock [C] ( [AB] / [C] / [AB] type)
Further, when the organopolysiloxane thioblock [C] is the side chain type [IV-3], a graft copolymer in which the block [AB] is added to the side chain of the organopolysiloxane thioblock [C] ( Comb-shaped copolymer)
In addition, when the organopolysiloxane thioblock [C] is the side chain double-ended type [IV-4], the block [AB] is added to both ends and side chains of the organopolysiloxane thioblock [C]. This is considered to be a star-type copolymer. However, these reactions may be presumed to have other block structures due to complicated radical termination reactions.

Organopolysiloxane thio block vinyl copolymer of the present invention, port Rieteru modified silicone block [A] is 1 to 80 wt%, preferably 5 to 50 wt% and polyoxyalkylene group-containing vinyl copolymer block [ B] is present in an amount of 5 to 98% by weight, preferably 10 to 90% by weight, and organopolysiloxane thioblock [C] is present in an amount of 1 to 80% by weight, preferably 5 to 50% by weight. .

Such a quantity depot Rieteru modified silicone block [A], and polyoxyalkylene group-containing vinyl copolymer block [B], an organopolysiloxane thio block [C] and the organopolysiloxane-thio block vinyl copolymer ( When it is contained in the silicone block vinyl copolymer.), The resulting organopolysiloxane thioblock vinyl copolymer tends to be excellent in film-forming property, coating film strength, and antifouling property.

  Such an organopolysiloxane thioblock vinyl copolymer according to the present invention, for example, has little impact on the environment and the human body when blended in an antifouling paint, and is excellent in antifouling properties and its sustainability. It is possible to form an antifouling coating film excellent in mechanical strength. In particular, with the organopolysiloxane thioblock vinyl copolymer of the present invention, a coating film excellent in properties such as the above mechanical strength can be formed even if silicone oil, paraffin component, etc. are blended, and the coating film It is possible to prepare paints such as antifouling paints and mold release agents that can form a coating film that can effectively suppress embrittlement.

[Production of organopolysiloxane thioblock vinyl copolymer]
In order to produce the organopolysiloxane thioblock vinyl copolymer of the present invention, for example,
A modified silicone represented by the above formula [I] and / or a modified silicone represented by the above formula [II];
The monomer (b1), that is, the (b1) polyoxyalkylene polymerizable unsaturated carboxylate [III] (e.g., methoxypolyethylene glycol monomethacrylate, in the formula [III], m + n = 2 to 100);
The monomer (b2), that is, at least one non-crosslinked polymerizable unsaturated carboxylic acid or ester thereof other than (b1) (e.g., methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meta)) ) Acrylate, isobornyl (meth) acrylate),
The monomer (b3), that is, a crosslinkable group-containing polymerizable unsaturated monomer (eg, γ-methacryloxypropyltrimethoxysilane, 4-hydroxybutyl acrylate) used as necessary;
The monomer (b4), that is, other polymerizable unsaturated monomer (eg, styrene, vinyl acetate, acrylonitrile) used as necessary,
Mercapto-modified polyorganosiloxane [IV-a] (eg, trade names “KF-2001, KP-358”, manufactured by Shin-Etsu Chemical Co., Ltd., mercapto-modified silicone) and radical generation such as radical polymerization initiators if necessary What is necessary is just to superpose | polymerize with a heat | fever or light according to normal reaction conditions in presence of a source.

In such a polymerization reaction, each monomer (including a macromonomer) may be used in an amount corresponding to the amount of each component unit in the organopolysiloxane thioblock vinyl copolymer. Specifically, The sum of the monomers (b1), (b2) and (b3) and (b4) ((b1) + (b2) + (b3) + (b4)) is usually 5 to 98% by weight, preferably 10 The modified silicone monomer [I] and / or the modified silicone monomer [II] is usually 1 to 80% by weight, preferably 5 to 50% by weight, and the mercapto-modified polyorganosiloxane [IV-a] is The amount is usually 1 to 80% by weight, preferably 5 to 50% by weight.

  The monomer (b1) with respect to 100% by weight of the total ((b1) + (b2) + (b3) + (b4)) of monomers for forming the polyoxyalkylene group-containing vinyl copolymer block [B]. Is usually 0.1 to 40% by weight, preferably 0.5 to 30% by weight, particularly preferably 1.0 to 20% by weight. The monomer (b2) is usually 60 to 99.9%. The monomer (b3) is usually 0 to 39% by weight, preferably 0 to 29% by weight, in an amount of 70% by weight, preferably 70 to 99.5% by weight, particularly preferably 80 to 99.0% by weight. Particularly preferably, the monomer (b4) is used in an amount of 0 to 19% by weight, usually in an amount of 0 to 39% by weight, preferably 0 to 29% by weight, particularly preferably 0 to 19% by weight.

  When each monomer is used in such an amount, the resulting organopolysiloxane thioblock vinyl copolymer tends to be excellent in film forming property, coating film strength, and antifouling property. This polymerization can be performed by various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization.

When the radical polymerization initiator is used, the radical polymerization initiator is usually 0.005 to 20 with respect to 100 parts by weight of the unsaturated monomers (monomers) in the above (b1) to (b4). Used in parts by weight. As such radical polymerization initiator, those generally used as radical polymerization reaction initiators can be widely used. Specifically, for example, 2, 2 ′
-Azobisisobutyronitrile (AIBN), 2,2'-azobisisovaleronitrile,
2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) (trade name “ABN-E”, manufactured by Nippon Hydrazine, azo compound), polydimethylsiloxane Polymer azo polymerization initiators (trade names “VPS-0501, VPS-1001”, manufactured by Wako Pure Chemical Industries, Ltd., azo compounds) and the like; benzoyl peroxide (BPO), hydroperoxide, t- And peroxides such as butyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate (trade name “Kaya Ester O” manufactured by Kayaku Akzo Co., Ltd.), and the like. These radical polymerization initiators may be used alone or in combination of two or more.

The solvent is not particularly limited as long as it has moderate volatility at room temperature and can dissolve the monomer used (including macromonomer) and the obtained organopolysiloxane thioblock vinyl copolymer. For example, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane and heptane; ethers such as diethyl ether, di-n-propyl ether, dibutyl ether, tetrahydrofuran and dioxane; ethyl acetate, propyl acetate and acetic acid Esters such as butyl and isobutyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and acetone; chlorinated hydrocarbons such as dichloromethane, trichloroethylene, tetrachloroethane and chloroform; methanol, ethanol, isopropanol, Nord, alcohols such as isobutanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, glycol derivatives such as propylene glycol monomethyl ether acetate-based solvents; and the like. These solvents (solvents) can be used alone or in combination of two or more.

These solvents include the modified silicone [I] and / or the modified silicone [II], the monomer (b1), the monomer (b2), the monomer (b3) and the monomer (b4) (including these macromonomers), Moreover, it can be used in an arbitrary amount with respect to a total of 100 parts by weight of the mercapto-modified polyorganosiloxane [IV-a], but for example, it is used in an amount of 10 to 1000 parts by weight, preferably 20 to 500 parts by weight. In the present invention, when solution polymerization is employed as the polymerization method, the organopolysiloxane thioblock vinyl copolymer obtained by the polymerization reaction can be used as it is without dilution and purification without solvent purification. ,preferable.

  The weight average molecular weight (Mw) measured by GPC of the organopolysiloxane thioblock vinyl copolymer thus obtained is usually 1,000 to 400,000, preferably 3,000 to 200,000. More preferably, it is 10,000 to 100,000. Moreover, the viscosity (mPa * s / 25 degreeC) is 50-100,000 normally in the 50 mass% solution, Preferably it is 100-20,000, The external appearance is a transparent or turbid solution normally.

<Application>
Such an organopolysiloxane thioblock vinyl copolymer (silicone block vinyl copolymer) according to the present invention is suitably used, for example, as a coating film forming component (vehicle component) for coatings represented by antifouling coatings. It is done. Other uses of the organopolysiloxane thioblock vinyl copolymer include, for example, anti-pasting paints, antifouling paints, anti-icing / snow accreting paints, graffiti-preventing paints, mold release materials, and the like.

  In addition, the antifouling paint composition (antifouling paint) containing the organopolysiloxane thioblock vinyl copolymer of the present invention as a resin component can be sufficiently prevented without blending an antifouling agent like conventional antifouling paints. The antifouling performance can be exhibited and the antifouling agent does not need to be added, but an antifouling agent may be added if necessary. Further, paints typified by antifouling paints containing such organopolysiloxane thioblock vinyl copolymers include water repellents described in Japanese Patent No. 2863562 as components containing various solvents and water repellent functional groups. Substances, leveling agents, ultraviolet absorbers, extender pigments, coloring pigments, sagging inhibitors, other color formers (film-forming components), plasticizers (eg chlorinated paraffin, etc.), usually paints (antifouling paints) Ingredients) may be blended with various components.

Examples of the water-repellent functional group-containing component include petrolatum, paraffin wax, paraffins such as liquid paraffin, dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, polyether-modified silicone oil, fluorosilicone oil, and terminal functional groups. Silicone oils such as silicone oils, long chain fatty acids such as caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid and their esters, beef tallow, lard, rosin, palm oil, palm oil, etc. Examples include natural fats and oils.

  The amount of such a water-repellent functional group-containing component is not particularly limited, but in the case of using the water-repellent functional group-containing component, it is usually from the viewpoint of film forming property, drying property, and adhesion of the resulting coating film. The amount of the present invention is usually 1 to 200 parts by weight, preferably 5 to 100 parts by weight per 100 parts by weight of the organopolysiloxane thioblock vinyl copolymer of the present invention (hereinafter also simply referred to as “copolymer”). Used in

  When preparing such an antifouling paint, conventionally known dispersing machines such as a high speed disper, a sand grind mill, a basket mill, a three roll, a ball mill, and an attritor can be used. Hereinafter, the antifouling coating composition, the coating film and the antifouling method according to the present invention will be described more specifically.

<Paint composition (paint), antifouling paint composition (antifouling paint)>
The copolymer composition and antifouling coating composition according to the present invention contain the organopolysiloxane thioblock vinyl copolymer as a coating film forming component or a vehicle. The coating film and antifouling coating film of the present invention are formed from this organopolysiloxane thioblock vinyl copolymer composition or antifouling coating composition.

  In the coating film formed from the organopolysiloxane thioblock vinyl copolymer in the present invention, the polysiloxane chain or polyoxyalkylene chain contained in the coating film has a surface that is difficult to adhere to the attached organism on the coating film surface. Since it forms, it is difficult for organisms in the water to adhere to the coating film, and even if it adheres, it can be easily removed, and excellent antifouling performance can be maintained over a long period of time.

  Such a copolymer composition and paint (including an antifouling paint composition) of the present invention may contain an optional component that is blended with a normal paint or the like. Hereinafter, the antifouling paint composition will be specifically exemplified and described. Examples of optional components that can be blended include antifouling agents, elution aids, plasticizers such as chlorinated paraffin, dehydrating agents (stabilizers), sagging and anti-settling agents, pigments, coating film forming components other than the above, solvents Various components such as may be included. Further, if necessary, a curing agent or a curing catalyst for crosslinking can be blended at the time of using the paint or preparing the paint.

<Anti-fouling agent>
In the antifouling paint composition of the present invention, the antifouling agent includes metallic copper, cuprous oxide, rhodan copper, basic copper sulfate, basic copper acetate, oxyquinoline copper, naphthenic acid copper, rosin acid copper, copper pyrithione. Zinc pyrithione, tetramethylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s- Examples include triazine, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,6-trichlorophenylmaleimide, pyridine-triphenylborane, and amine-triphenylborane.

<Elution aid>
As the dissolution aid, various compounds having a surfactant action that assist in the surface migration of the water repellent to be blended or that can effectively and slowly release the antifouling agent can be used. For example, monobasic acids such as rosin and naphthenic acid, various polyalkylene-modified products and the like can be used as necessary.

<Plasticizer>
As plasticizers, regular phosphate esters, chlorinated paraffins, phthalate esters, adipic acid esters, etc. are usually used for paints in order to give flexibility to coating films and improve crack resistance and adhesion. Plasticizers that can be used may also be used.

  In the antifouling paint composition according to the present invention, these plasticizers are contained in an amount of 0 to 50 parts by weight with respect to 100 parts by weight of the silicone block vinyl copolymer (solid content), if necessary. May be.

<Dehydrating agent (stabilizer)>
The dehydrating agent (stabilizer) is a storage stability of the composition (antifouling paint) especially when the component unit (b3) derived from the crosslinkable polymerizable unsaturated monomer contains an alkoxysilyl group or an isocyanate group. The property can be further improved.

Specific examples of such dehydrating agents (stabilizers) include orthoesters such as anhydrous gypsum (CaSO ₄ ), synthetic zeolite-based adsorbents (trade name: molecular sieve, etc.), methyl orthoformate, and methyl orthoacetate. , Orthoborate esters, silicates and isocyanates (trade name: additive TI). In the antifouling paint composition according to the present invention, the dehydrating agent is included in an amount of 0 to 40 parts by weight with respect to 100 parts by weight of the silicone block vinyl copolymer (solid content), if necessary. Also good.

<Anti-sagging / Anti-settling agent (fading agent)>
In the present invention, various anti-sagging / anti-settling agents (adhesives) may be added to improve thick coatability and anti-sagging properties during coating and to prevent settling of solvent-insoluble components (pigments etc.) used as necessary. good.

Anti-sagging and anti-settling agents (fading agents) include organoclay Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonate salts, polyethylene wax, amide wax, hydrogenated castor oil wax system Polyamide wax and mixtures thereof, synthetic fine powder silica, oxidized polyethylene wax, and the like. Polyamide wax, synthetic fine powder silica, oxidized polyethylene wax, and organic viscosity system are preferably used. Examples of such anti-sagging and anti-settling agents are those marketed under the trade names such as “DISPARON 305” and “DISPARON 4200-20” manufactured by Enomoto Kasei Co., Ltd. and “DISPARON A630-20X”. Is mentioned. Such an anti-sagging / anti-settling agent may be contained in the antifouling coating composition in an amount of, for example, 0 to 10% by weight, if necessary.

<Pigment>
As the pigment other than the antifouling agent, conventionally known various organic or inorganic colored or extender pigments can be used. Examples of organic pigments include carbon black, phthalocyanine blue, and bitumen. Examples of inorganic pigments include titanium white, bengara, barite powder, silica, calcium carbonate, talc, barium sulfate, zinc white (ZnO, zinc oxide), lead white, red lead, and zinc dust. Such various pigments may be blended in the antifouling coating composition in an amount of about 0 to 45% by weight as required.

<Other coating film forming components>
The antifouling coating composition of the present invention may contain a resin other than the silicone block vinyl copolymer of the present invention as a coating film forming component. Other coating film forming components include, for example, acrylic resin, acrylic silicone resin, polyester resin, fluorine resin, polybutene resin, silicone rubber, urethane resin (rubber), polyamide resin, vinyl chloride copolymer resin, and chlorinated rubber (resin). , Chlorinated olefin resin, styrene-butadiene copolymer resin, ethylene
Examples thereof include vinyl acetate copolymer resins, vinyl chloride resins, coumarone resins, trialkylsilyl acrylate (co) polymers (silyl resins), petroleum resins, ketone resins, formaldehyde resins, and polyvinyl alkyl ether resins.

These “other coating film forming components” other than the silicone block vinyl copolymer of the present invention may be contained in the antifouling coating composition in an amount of 95% by weight or less.
<Solvent>
In the antifouling paint of the present invention, the various components as described above are dissolved or dispersed in a solvent. As the solvent used here, for example, various solvents such as aliphatic, aromatic, ketone, ester, ether and the like which are usually blended in antifouling paints are used. Examples of the aromatic solvent include xylene and toluene. Examples of the ketone solvent include MIBK. Examples of the ester solvent include butyl acetate. Examples of the ether solvent include Examples thereof include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (PMAC).

In the present invention, the amount of these solvents added is not particularly limited.
<Curing agent / Curing catalyst>
In the present invention, the organopolysiloxane thioblock copolymer of the present invention or the copolymer is contained by crosslinking the crosslinkable functional group in the component unit (b3) derived from the crosslinkable polymerizable unsaturated monomer. A coating film formed by curing a coating film formed by applying a paint, or by promoting a crosslinking reaction including self-crosslinking and applying the organopolysiloxane thioblock copolymer of the present invention or the coating composition containing the copolymer. In order to cure, a known curing agent and curing catalyst can be appropriately used.

  Specifically, for example, when (b3) contains a hydroxyl group, a commercially available isocyanate-based curing agent or melamine-based curing agent can be used. In (b3), an alkoxysilyl group or aryloxy group can be used. When silyl group or silanol group is included, alkyl silicates can also be used as curing agent, and further promote self-crosslinking and tin, aluminum, titanium-based to promote crosslinking reaction using curing agent When (b3) contains an epoxy group, commercially available various amines, thiols, cationic initiators, and epoxy curing agents can be used. When an isocyanate group is included in b3), a polyol component such as acrylic polyol or a polyamino compound can be used as a curing agent, and it is further moisture-curing. A curing catalyst such as tin, aluminum, titanium, etc. can be used to promote the self-crosslinking of the resin and to promote the crosslinking reaction using a curing agent, and when (b3) contains a carboxyl group, Polyglycidyl compounds, polyvalent metals and their salts can be used as curing agents. When (b3) contains a (meth) acryloxy group or vinyl group, a radical generator is used as a curing catalyst. Alternatively, polyamines and polymercapto compounds can be used as curing agents.

<Manufacture of antifouling paint composition>
The antifouling coating composition of the present invention can be produced by appropriately utilizing conventionally known methods. For example, the silicone block vinyl copolymer solution of the present invention obtained by solution polymerization can be used as it is as an antifouling coating composition, and a water-repellent component may be added and mixed as necessary. , Dissolution aids, plasticizers, dehydrating agents (stabilizers), anti-sagging / precipitating agents, pigments, other film-forming components, solvents, etc., once in a prescribed ratio or in any order, stirring and mixing Then, it may be uniformly dissolved and decomposed.

  The antifouling coating composition obtained in this way may be mixed with a crosslinking agent or a curing catalyst as necessary, applied to the surface of the substrate to be coated and then dried, and when the coating is cured. Can be used practically.

<Use of antifouling paint composition>
The antifouling paint composition according to the present invention can form a coating film having a stable antifouling performance for a long time. For example, ships, fishing materials (eg, ropes, fishing nets, floats, buoys), thermal power / nuclear power plants Antifouling coating with excellent antifouling properties if applied to the surface of various base materials such as underwater structures such as water supply and drainage ports, gulf roads, submarine tunnels, harbor facilities, canals and waterways, and sludge diffusion prevention films for marine civil engineering work Ships or underwater structures coated with a membrane can be obtained.

  That is, the antifouling coating film obtained by applying and curing the antifouling coating composition of the present invention on the surface of various substrates continuously adheres to aquatic organisms such as Aosa, Barnacles, Aonori, CellPura, Oyster, Fusakomushi, etc. for a long time. It has excellent antifouling properties such as In particular, the antifouling coating composition adheres well to the surfaces of these substrates even when the substrate is steel, FRP, wood, aluminum alloy or the like. In addition, the antifouling coating composition may be overcoated on the surface of a coating film that has already been coated or on the surface of an existing antifouling coating film.

  In addition, when the antifouling coating composition of the present invention is applied to the surface of an underwater structure, it is possible to prevent adhesion of marine organisms and to maintain the function of the structure for a long period of time. Moreover, if the antifouling paint composition of the present invention is applied to fishing materials such as fishing nets or fishing gears, the fishing nets or fishing gears can be prevented from being polluted, and the risk of environmental pollution is extremely low.

  The antifouling coating film of the present invention, that is, the coating film applied to the surface of the water contact portion of the ship or underwater structure is formed from the antifouling coating composition described above, and has a very low risk of environmental pollution. Excellent long-term antifouling properties against organisms attached to structures.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by this Example.

The compounding components and test methods used in the examples and comparative examples are as follows.
<Raw material>
The raw materials used are as follows.

<Measurement conditions>
The measurement conditions for GCP and IR are as follows.
[GPC measurement conditions]
Equipment: HLC-8120GPC manufactured by Tosoh Corporation
Column: Super H2000 + H4000 6mm ID, 15cm, manufactured by Tosoh Corporation
Eluent: THF
Flow rate: 0.5 ml / min
Detector: RI
Column thermostat temperature: 40 ° C.

[IR measurement conditions]
Apparatus: PerkinElmer Spctrum One FT-IR
Measuring method: KBr cell, coating method.

<Synthesis of polyether-modified silicone>
[Synthesis Example 1]
In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, an OH group-containing EO-modified silicone (trade name “FZ-2191”, manufactured by Nippon Unicar Co., Ltd., solid content 100%, OH equivalent 1152) 1, 152 parts by weight and 0.59 parts by weight of p-methoxyphenol were charged, and the temperature was raised to 60 ° C. Next, 31 parts by weight of 2-methacryloyloxyethyl isocyanate (trade name “Karenz MOI”, manufactured by Showa Denko KK) was added and reacted at 60 ° C. for 1 hour. As a result of IR analysis of the reaction product, the isocyanate group absorption peak disappeared completely.

  Thereafter, 131 parts by weight of butyl acetate was further added to obtain a copolymer S-1 solution. The appearance of this copolymer S-1 solution is transparent, NV (heating residue after drying for 3 hours in a hot air dryer at 105 ° C.) is 90% by weight, and the viscosity is 330 mPa · s / 25 ° C. The weight average molecular weight (Mw) of the copolymer S-1 was 11,510.

[Synthesis Example 2]
In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, an OH group-containing EO-modified silicone (trade name “KF-353A”, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%, OH equivalent 880) 880 1 part by weight, 23.3 parts by weight of 2-methacryloyloxyethyl isocyanate (trade name “Karenz MOI”, Showa Denko KK) and 0.45 parts by weight of p-methoxyphenol were added, and the temperature was raised to 100 ° C. Allowed to react for 8 hours. As a result of IR analysis of the reaction product, the isocyanate group absorption peak disappeared completely.

  Thereafter, 100 parts by weight of butyl acetate was further added to obtain a copolymer S-2 solution. The appearance of this copolymer S-2 solution is transparent, NV (heating residue after drying for 3 hours in a hot air dryer at 105 ° C.) is 90% by weight, and the viscosity is 720 mPa · s / 25 ° C. The weight average molecular weight (Mw) of the copolymer S-2 was 18,020.

[Example 1]
A reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping device, and a reflux condenser was charged with 30.66 parts by weight of butyl acetate and 16.7 parts by weight of xylene at 100 ° C. in a nitrogen gas atmosphere. The temperature was raised to. Then, as shown in Table 2,
42.5 parts by weight of methyl methacrylate (MMA),
15 parts by weight of n-butyl methacrylate (BMA),
10 parts by weight of 2-ethylhexyl acrylate (2EHA),
1. Methoxypolyethylene glycol methacrylate (trade name “NK ester M-230G”, manufactured by Shin-Nakamura Chemical Co., Ltd., —C ₂ H ₄ —O—unit number = 23 (average value), solid content: 100% by weight) 5 parts by weight,
5 parts by weight of γ-methacryloxypropyltrimethoxysilane (trade name “A-174”, manufactured by Nihon Unicar)
44.44 parts by weight of the copolymer S-1 solution (NV 90%) synthesized in Synthesis Example 1 and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator (trade name “ABN-E”)
"Nippon Hydrazine Co., Ltd.) 2.2 parts by weight of mixture A;
Mercapto-modified silicone (trade name “KF-2001”, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight Mw: 9200, solid content: 100% by weight, SH group position is side chain type) 25 parts by weight and butyl acetate 12 Then, 5 parts by weight of the mixture B was simultaneously added dropwise to the reaction vessel while maintaining the internal temperature of 100 ° C.

The liquid mixture A was dripped over 3 hours, and the mixture B was dripped over 1.5 hours.
One hour after completion of the dropwise addition of the mixture A, a further butyl acetate solution of ABN-E (20% by weight)
After adding 1 part by weight 3 times every 45 minutes, the mixture was stirred while being kept warm for 1.5 hours to obtain a copolymer A-1 solution. The appearance of this copolymer A-1 solution is transparent, NV (heating residue after drying for 3 hours in a hot air dryer at 105 ° C.) is 66.5% by weight, and the viscosity is 3,790 mPa · s / The temperature was 25 ° C, and the copolymer A-1 weight average molecular weight (Mw) was 56,740.

  Table 2 shows the blending composition (parts by weight), the catalyst, the solvent, the reaction temperature, etc. at the time of preparing the copolymer A-1, and the properties of the obtained copolymer A-1. Table 2 summarizes the contents of the symbols (product names) appearing in the following table, the manufacturer, and the like. The GPC chromatogram of copolymer A-1 is shown in FIG. 1, and the IR spectrum chart is shown in FIG.

[Examples 2 to 12]
Copolymer A-2 to A-12 solutions were synthesized in the same manner as in Example 1 except that the formulation was changed as shown in Tables 2 and 3. The physical properties of each copolymer were evaluated in the same manner as in Example 1 above. In addition to blending composition of raw materials (indicated by weight), catalyst, solvent, reaction temperature, etc. during the production of copolymer A-2 to A-12 solution, properties of copolymer A-2 to A-12 solution, etc. Are shown in Table 2 and Table 3.

In addition, GPC chromatograms and IR spectrum charts of the copolymers A-2 to A-12 are shown in FIGS.
[Comparative Examples 1 and 2]
A copolymer H-1 solution and a copolymer H-2 solution were synthesized in the same manner as in Example 1 except that the blending composition was changed as shown in Table 2. The physical properties of each copolymer were evaluated in the same manner as in Example 1 above. In addition to the composition of raw materials (in parts by weight), catalyst, solvent, reaction temperature, etc., during the production of copolymer H-1 solution and copolymer H-2 solution, polymer H-1 solution and copolymer weight Table 2 shows properties of the combined H-2 solution.

Next, antifouling paint compositions having the composition shown in Tables 4 to 7 were produced by the following method.
<Composition composed only of liquid components>
[Example T-1]
As shown in Table 4,
100 parts by weight of copolymer A-1 solution (NV = 90% by weight)
6.1 parts by weight of silicone oil, and 10.7 parts by weight of xylene and 2.7 parts by weight of methyl isobutyl ketone (MIBK) as a solvent,
Was thoroughly stirred and mixed using a high speed disper and filtered through a 120 mesh filter to prepare an antifouling paint composition. In addition, 0.5 weight part of the catalyst in Table 4 was not mixed at this stage, but was mixed immediately before the antifouling evaluation as described later.

[Examples T-2 to T-12, Comparative Examples HT-1 to HT-12]
As shown in Tables 4 and 5, an antifouling coating composition was prepared in the same manner as in Example T-1, except that the type of the copolymer solution and the amount of each component were changed. In addition, 0.5 weight part of the catalysts in Tables 4 and 5 were not mixed at this stage, but were mixed immediately before the antifouling evaluation as described later.

<Composition containing solid components such as pigment>
[Example T-13]
As shown in Table 6,
100 parts by weight of copolymer A-1 solution (NV = 90% by weight)
6.1 parts by weight of silicone oil,
0.7 parts by weight of KF-96-1000CS as an antifoaming agent 12 parts by weight of xylene and 2.7 parts by weight of methyl isobutyl ketone (MIBK) as a solvent
As a pigment, 1.3 parts by weight of a petal (trade name “Gekkou BB”, manufactured by Nippon Petrochemical Industry Co., Ltd.), 0.7 part by weight of Fuji First Red 2305W and titanium oxide (trade name “TCR-73”,
4 parts by weight (manufactured by Sakai Chemical Co., Ltd.) and 8 parts by weight of Dispalon 6900-10X as an additive were placed in a paint shaker using glass beads as a medium, shaken for 2 hours, and then filtered through a 120 mesh filter An antifouling paint composition was prepared. In addition, 0.5 part by weight of the catalyst (ALCH-TB) in Table 6 was not mixed at this stage, but was mixed immediately before the antifouling evaluation as described later.

[Examples T-14 to T-24, Comparative Examples HT-13 to HT-24]
As shown in Tables 6 and 7, an antifouling paint composition was prepared in the same manner as in Example T-13, except that the type of copolymer solution and the amount of each component were changed. In addition, 0.5 part by weight of the catalyst (ALCH-TB) in Tables 6 and 7 was not mixed at this stage, but was mixed immediately before the antifouling evaluation as described later.

<Evaluation of antifouling property>
The antifouling properties of the above antifouling coating compositions were evaluated. The results are shown in Tables 4-7.
The antifouling property was evaluated using the following method. An epoxy base coat is applied to a 100 mm x 300 mm x 5 mm vinyl chloride plate using an air spray so that the dry film thickness is 100 μm, dried at room temperature for 2 weeks, and then the dry film thickness is 150 μm using an applicator. After coating and drying in the room for a week, it was immersed in a place 1 m below the surface of the water from a cocoon installed in Hiroshima Bay, and the state of attachment of organisms for 18 months was visually observed. In addition, Examples T-1 to 3, T-7 to 9, T-13 to 15 and T-19 to 21, and Comparative Examples HT-1 to 3, HT-7 to 9, HT-13 to 15 and HT In -19 to 21, each antifouling paint composition and the amount of catalyst described in Tables 4 to 7 were thoroughly mixed immediately before coating.

  The evaluation was performed using the adhesion area (%) of the macro organism as an index.

FIG. 1 is a GPC chromatogram of copolymer A-1. FIG. 2 is an IR spectrum chart of the copolymer A-1. FIG. 3 is a GPC chromatogram of copolymer A-2. FIG. 4 is a chart of the IR spectrum of copolymer A-2. FIG. 5 is a GPC chromatogram of copolymer A-3. FIG. 6 is a chart of an IR spectrum of copolymer A-3. FIG. 7 is a GPC chromatogram of copolymer A-4. FIG. 8 is a chart of the IR spectrum of copolymer A-4. FIG. 9 is a GPC chromatogram of copolymer A-5. FIG. 10 is an IR spectrum chart of Copolymer A-5. FIG. 11 is a GPC chromatogram of copolymer A-6. FIG. 12 is an IR spectrum chart of the copolymer A-6. FIG. 13 is a GPC chromatogram of copolymer A-7. FIG. 14 is an IR spectrum chart of Copolymer A-7. FIG. 15 is a GPC chromatogram of copolymer A-8. FIG. 16 is an IR spectrum chart of Copolymer A-8. FIG. 17 is a GPC chromatogram of copolymer A-9. FIG. 18 is an IR spectrum chart of Copolymer A-9. FIG. 19 is a GPC chromatogram of Copolymer A-10. FIG. 20 is an IR spectrum chart of Copolymer A-10. FIG. 21 is a GPC chromatogram of Copolymer A-11. FIG. 22 is an IR spectrum chart of the copolymer A-11. FIG. 23 is a GPC chromatogram of Copolymer A-12. FIG. 24 is an IR spectrum chart of Copolymer A-12.

Claims (20)

And 1 to 80 wt% of the lower Kipo Rieteru modified silicone block [A], and 5 to 98 wt% of the following polyoxyalkylene group-containing vinyl copolymer block [B], from 1 to 80 wt% of the following organopolysiloxanes A thioblock [C] (provided that the sum of [A], [B] and [C] is 100% by weight) ;
An organopolysiloxane thioblock vinyl copolymer having a weight average molecular weight (Mw) measured by GPC of 1,000 to 400,000;
[A] Component unit (a1) derived from a modified silicone represented by the following formula [I] and / or Component unit (a2) derived from a modified silicone represented by the following formula [II]
A polyether-modified silicone block comprising:

[In Formula [I], each R ¹¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms,
R ¹² each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms,
R ¹³ and R ¹⁴ may be the same or different from each other and each independently represents an alkylene group having 2 to 4 carbon atoms,
R ¹⁵ represents a polymerizable unsaturated hydrocarbon group-containing group,
X represents a divalent hydrocarbon group or -YNHCOOZ-;
Y represents a diisocyanate compound residue;
Z represents a divalent hydrocarbon group.
A, b, c, d, and e each represent a positive integer. ],

[In the formula [II], each R ²¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms,
R ²² each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms,
R ²³ and R ²⁴ may be the same or different from each other and each independently represents an alkylene group having 2 to 4 carbon atoms;
R ²⁵ represents a polymerizable unsaturated hydrocarbon group-containing group,
X, Y and Z are the same as X, Y and Z, respectively.
P, q, r, and s each represent a positive integer. ],
[B] A component derived from a polyoxyalkylene polymerizable unsaturated carboxylate represented by the following formula [III] and formed by forming an ester with a polymerizable unsaturated carboxylic acid at least at one end of a polyoxyalkylene compound unit Unit (b1) and / or Component unit (b2) derived from at least one non-crosslinked polymerizable unsaturated carboxylic acid or ester thereof other than the component unit (b1)
A polyoxyalkylene group-containing vinyl copolymer block having:
_{^{R 34 - [OR 31] m}} - [OR 32] n -OCOR 33 ··· [III]
[In the formula [III], R ³¹ and R ³² represent a divalent hydrocarbon group which may be the same or different from each other;
R ³³ represents a polymerizable unsaturated hydrocarbon group-containing group,
R ³⁴ represents a hydrogen atom, a monovalent hydrocarbon group that may have a polymerizable unsaturated bond, or a monobasic or dibasic organic carboxylic acid residue R that may have a polymerizable unsaturated bond. ³⁵ indicates CO-
R ³⁵ represents an organic group which may have a polymerizable unsaturated bond,
m and n each represent a positive integer. ],
[C] an organopolysiloxane thioblock comprising a component unit represented by the following formula [IV];

[In the formula [IV], each R ⁴¹ independently represents a hydrocarbon group having 1 to 10 carbon atoms,
R ⁴² , R ⁴³ and R ⁴⁴ each independently represent R ⁴¹ or a divalent thioorganic group having 1 to 20 carbon atoms;
t and u each represent a positive integer. ]. The polyoxyalkylene group-containing vinyl copolymer block [B] further comprises 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, (poly) caprolactone (meth) acrylate, 2-hydroxybutyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meta ) Acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethoxyethoxysilane, vinyltriacetoxysilane, p-trimethoxysilylstyrene, p-triethoxysilyl Tylene, p-trimethoxysilyl-α-methylstyrene, p-triethoxysilyl-α-methylstyrene, vinyltrimethoxysilane, vinyltriethoxysilane, N-β (N-vinylbenzylaminoethyl-γ-aminopropyl) Trimethoxysilane / hydrochloride, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acryloyl isocyanate and 2- (meth) acryloxy The organopolysiloxane thioblock vinyl copolymer according to claim 1, which has a component unit (b3) derived from a crosslinkable polymerizable unsaturated monomer selected from the group consisting of ethyl isocyanate . The polyoxyalkylene group-containing vinyl copolymer block [B] further comprises styrene, α-methylstyrene, vinyl acetate, vinyl propionate, N, N-dimethylacrylamide, dimethylaminoethylacrylamide, ethyl vinyl ether, isobutyl vinyl ether, and The organopolysiloxane thioblock vinyl copolymer according to claim 1 or 2, which has a component unit (b4) derived from another polymerizable unsaturated monomer selected from the group consisting of acrylonitrile . The content of the above Kipo Rieteru modified silicone block [A] is from 5 to 50 wt%, the content of the polyoxyalkylene group-containing vinyl copolymer block [B] is 10 to 90 wt%, the organopolysiloxane content of 5-50% by weight of thio block [C] (provided that, [a], [B] and [C] total to 100 wt%.) of claims 1-3, characterized in that the The organopolysiloxane thioblock vinyl copolymer according to any one of the above. Upper Kipo Rieteru modified silicone block [A] is any of the claims 1-4 where the weight-average molecular weight measured by GPC (Mw) is equal to or derived from the modified silicone is 300 to 100,000 The organopolysiloxane thioblock vinyl copolymer described in 1. Polymerizable group (meth) organopolysiloxane thio block vinyl copolymer according to any one of claims 1 to 5, wherein the acryloyl group of the upper Kipo Rieteru modified silicone block [A]. The organopolysiloxane thio block [C] is, according to claim 1-6, characterized in that the weight average molecular weight measured by GPC (Mw) is derived from a mercapto-modified polyorganosiloxanes is 300 to 100,000 The organopolysiloxane thioblock vinyl copolymer according to any one of the above. Claim upper Kipo Rieteru modified silicone block [A] is characterized by having at least one group selected from the group consisting of polyoxyethylene groups, polyoxypropylene groups and poly (oxyethylene-oxypropylene) group The organopolysiloxane thioblock vinyl copolymer according to any one of 1 to 7 . The non-crosslinked polymerizable unsaturated carboxylic acid or a component unit derived from the ester (b2) is, according to claim 1-8, characterized in that the component unit derived from the (meth) acrylic acid or its ester The organopolysiloxane thioblock vinyl copolymer according to any one of the above. Constituent units derived from the polyoxyalkylene polymerizable unsaturated carboxylate (b1) is, to any one of claims 1 to 9, characterized in that a constituent unit derived from a polyoxyalkylene (meth) acrylate The organopolysiloxane thioblock vinyl copolymer described. An antifouling paint composition comprising the organopolysiloxane thioblock vinyl copolymer according to any one of claims 1 to 10 as a vehicle component. An organopolysiloxane thioblock vinyl copolymer composition comprising the organopolysiloxane thioblock vinyl copolymer according to any one of claims 1 to 10 and a water repellent functional group-containing component. The organopolysiloxane thioblock vinyl copolymer composition according to claim 12 , wherein the water repellent functional group-containing component is silicone oils and / or paraffins. An antifouling paint composition comprising the organopolysiloxane thioblock vinyl copolymer composition according to claim 12 or 13 . Furthermore, an antifouling agent is contained, The antifouling coating composition of Claim 11 or 14 characterized by the above-mentioned. An antifouling coating film formed from the antifouling coating composition according to claim 11 , 14 or 15 or the organopolysiloxane thioblock vinyl copolymer composition according to claim 12 or 13 . A substrate coated with the antifouling coating film according to claim 16 . The underwater structure by which the surface of the base material was coat | covered with the antifouling coating film of Claim 16 . The ship by which the surface of the ship base material was coat | covered with the antifouling coating film of Claim 16 . A substrate antifouling method comprising coating the surface of a substrate with the antifouling coating film according to claim 16 .

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