WO2017051922A1 - (メタ)アクリル系共重合体、重合体溶液、重合体含有組成物、防汚塗料組成物及び(メタ)アクリル系共重合体の製造方法 - Google Patents
(メタ)アクリル系共重合体、重合体溶液、重合体含有組成物、防汚塗料組成物及び(メタ)アクリル系共重合体の製造方法 Download PDFInfo
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Definitions
- the present invention relates to a (meth) acrylic copolymer, a polymer solution, a polymer-containing composition, an antifouling coating composition, and a method for producing a (meth) acrylic copolymer.
- This application claims priority based on Japanese Patent Application No. 2015-188349 filed in Japan on September 25, 2015 and Japanese Patent Application No. 2015-190946 filed on September 29, 2015 in Japan. , The contents of which are incorporated herein.
- antifouling paints are applied to offshore structures and ships for the purpose of preventing adhesion of marine organisms that cause corrosion of a portion in contact with seawater and a decrease in navigation speed.
- Self-polishing antifouling paints are known as antifouling paints.
- the self-polishing antifouling paint typically contains a hydrolyzable resin and an antifouling agent.
- the coating film obtained from this antifouling paint is dissolved in seawater and the surface is renewed (self-polishing), and the antifouling components are always exposed on the surface of the paint film. Demonstrate.
- a resin composition containing a metal-containing polymer as described below As self-polishing antifouling paints, for example, those using a resin composition containing a metal-containing polymer as described below have been proposed. Such a resin composition is mixed with an antifouling agent or the like to form an antifouling paint.
- the metal-containing polymer contained in these resin compositions has hydrolyzability, and a coating film containing the polymer exhibits self-polishing properties.
- a resin composition obtained by copolymerization with a saturated monomer Patent Document 1.
- a vinyl polymer obtained by polymerizing a carboxy group-containing ethylenically unsaturated monomer, a divalent metal-containing ethylenically unsaturated monomer, and a macromonomer having a radical polymerizable group in a specific procedure A resin composition dispersed in a dispersion medium containing water (Patent Document 2).
- self-polishing antifouling paints for example, those using a composition for antifouling paints containing a vinyl polymer having a hemiacetal ester group and / or a hemiketal ester group in the side chain and an organic solvent have been proposed.
- Patent Document 3 Such an antifouling paint composition is mixed with an antifouling agent or the like to form an antifouling paint.
- the vinyl polymer has hydrolyzability, and a coating film containing the vinyl polymer exhibits self-polishing properties.
- VOC volatile organic compounds
- JP 2002-012630 A International Publication No. 2013/108880 Japanese Patent Laid-Open No. 4-103671
- the coating film formed from the antifouling paint using the resin composition of Patent Document 1 tends to lack hardness and water resistance. Therefore, the long-term antifouling effect of the coating film is not always sufficient. Furthermore, this resin composition has a problem in that it is difficult to achieve high solidification because it tends to be highly viscous and difficult to prepare and paint an antifouling paint if the content of the organic solvent is reduced to attempt high solid differentiation.
- the coating film formed from the resin composition of Patent Document 2 has insufficient water resistance. In addition, there is a tendency that the dissolution rate is slow (the degree of wear is low). Therefore, the long-term antifouling effect of the coating film is not always sufficient.
- the antifouling paint film using the antifouling paint composition of Patent Document 3 tends to lack one or more of hardness and water resistance.
- the viscosity of the antifouling coating composition is lowered, the hardness of the coating film tends to be insufficient. Due to the low hardness of the coating film, when it is temporarily placed after painting, a trace remains due to contact with the gantry, and the coating film tends to be defective.
- this antifouling paint composition contains a large amount of an organic solvent, and the antifouling paint using this antifouling paint composition has a high VOC content. If the content of the organic solvent is reduced, the VOC is reduced, but the viscosity increases due to an increase in the solid content, making it difficult to prepare and paint the antifouling paint.
- An object of the present invention is to provide an antifouling coating composition capable of forming a coating film excellent in water resistance and hardness, a (meth) acrylic copolymer, a polymer solution and a polymer suitable for obtaining the antifouling coating composition.
- the object is to provide a coalescence-containing composition and a method for producing the (meth) acrylic copolymer.
- Structural unit (A1) having at least one structure (I) selected from the group consisting of structures represented by the following formula (1), the following formula (2) or the following formula (3), and a triorgano A (meth) acrylic copolymer having at least one structural unit selected from the group consisting of a structural unit (A2) having a silyloxycarbonyl group and a structural unit (B) derived from the macromonomer (b).
- X represents —O—, —S— or —NR 14 —
- R 14 represents a hydrogen atom or an alkyl group
- R 1 and R 2 represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively.
- R 3 and R 5 each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group, and R 4 and R 6 each represents an alkylene group having 1 to 10 carbon atoms.
- a structural unit (A3) having at least one structure (III) selected from the group consisting of structures represented by the following formula (4) or (5), and a structural unit derived from the macromonomer (b) ( B), and a (meth) acrylic copolymer having An organic solvent, and A polymer solution having a viscosity at 25 ° C. of 5 ⁇ 10 4 mPa ⁇ s or less.
- a polymer-containing composition comprising the polymer solution according to [2], wherein the content of the organic solvent is 30% by mass or more based on the total amount excluding the (meth) acrylic copolymer. .
- the macromonomer (b) is a macromonomer having two or more structural units represented by the following formula (b ′) and having a number average molecular weight of 500 to 50,000 (meta) ) Acrylic copolymer.
- R 41 represents a hydrogen atom, a methyl group or CH 2 OH
- R 42 represents OR 43 , a halogen atom, COR 44 , COOR 45 , CN, CONR 46 R 47 or R 48.
- R 43 to R 47 each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted group; Having a heteroaryl group, an unsubstituted or substituted non-aromatic heterocyclic group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, or an unsubstituted or shows the organosilyl group having a substituent, R 48 is an aryl group or an unsubstituted or substituted group having an unsubstituted or substituted het An aryl group.) [6] The polymer according to [2], wherein the macromonomer (b) is a macromonomer having two or more structural units represented by the following formula (b ′) and having a number average molecular weight of 500 to
- R 41 represents a hydrogen atom, a methyl group or CH 2 OH
- R 42 represents OR 43 , a halogen atom, COR 44 , COOR 45 , CN, CONR 46 R 47 or R 48.
- R 43 to R 47 each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted group; Having a heteroaryl group, an unsubstituted or substituted non-aromatic heterocyclic group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, or an unsubstituted or shows the organosilyl group having a substituent, R 48 is an aryl group or an unsubstituted or substituted group having an unsubstituted or substituted het An aryl group.) [7] The macromonomer (b) is a macromonomer having two or more structural units represented by the following formula (b ′) and having a number average molecular weight of 500 to 50,000, [3] or [4]
- R 41 represents a hydrogen atom, a methyl group or CH 2 OH
- R 42 represents OR 43 , a halogen atom, COR 44 , COOR 45 , CN, CONR 46 R 47 or R 48.
- R 43 to R 47 each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted group; Having a heteroaryl group, an unsubstituted or substituted non-aromatic heterocyclic group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, or an unsubstituted or shows the organosilyl group having a substituent
- R 48 is an aryl group or an unsubstituted or substituted group having an unsubstituted or substituted het An
- the (meth) acrylic copolymer has the structural unit (A1), And further comprising at least one alkenyl compound selected from the group consisting of a compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following formula (13): [8] The polymer-containing composition according to [8]. (Wherein X represents —O—, —S— or —NR 14 —, R 14 represents a hydrogen atom or an alkyl group, and R 7 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms).
- R 8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 9 and R 11 each represents an alkyl group, a cycloalkyl group or an aryl group having 1 to 20 carbon atoms
- R 10 represents a single bond Or an alkylene group having 1 to 9 carbon atoms
- R 12 represents an alkylene group having 1 to 9 carbon atoms.
- the antifouling agent comprises cuprous oxide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, triphenylborane and medetomidine
- the antifouling paint composition according to [11] comprising at least one selected from [13]
- R 3 and R 5 each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group;
- R 4 and R 6 each represents an alkylene group having 1 to 10 carbon atoms;
- R 31 represents a hydrogen atom or a methyl group, and
- R 32 represents an organic acid residue other than a (meth) acryloyloxy group.
- an antifouling coating composition capable of forming a coating film excellent in water resistance and hardness, a (meth) acrylic copolymer, a polymer solution and a polymer suitable for obtaining the antifouling coating composition.
- a coalescence-containing composition and a method for producing the (meth) acrylic copolymer can be provided.
- VOC means an organic compound (volatile organic compound) that easily volatilizes at normal temperature and pressure.
- the “structural unit” may be directly formed from a monomer by a polymerization reaction, and by treating the polymer obtained by the polymerization reaction, one of the structures of the structural unit of the polymer is included. It may be a structural unit whose part is converted into another structure.
- “Monomer” means a polymerizable compound (polymerizable monomer).
- (Meth) acrylate is a generic term for acrylate and methacrylate
- (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid
- (meth) acryloyl group is an acryloyl group and a methacryloyl group.
- (Meth) acrylonitrile” is a generic term for acrylonitrile and methacrylonitrile
- (meth) acrylamide is a generic term for acrylamide and methacrylamide.
- the “(meth) acrylic copolymer” means a copolymer in which at least a part of the structural unit is a structural unit derived from a (meth) acrylic monomer.
- the (meth) acrylic polymer may further have a structural unit derived from a monomer other than the (meth) acrylic monomer (for example, a vinyl monomer such as styrene).
- a monomer other than the (meth) acrylic monomer for example, a vinyl monomer such as styrene.
- (Meth) acrylic monomer means a monomer having a (meth) acryloyl group.
- “Viscosity” means a value measured by a B-type viscometer unless otherwise specified.
- the first aspect of the present invention is a macromonomer comprising at least one structural unit selected from the group consisting of the structural unit (A1) having the structure (I) and the structural unit (A2) having a triorganosilyloxycarbonyl group.
- (B) a structural unit (B) derived from (meth) acrylic copolymer (hereinafter also referred to as “copolymer (A-1)”).
- the copolymer (A-1) can further have a structural unit (A3) having the structure (III), if necessary.
- the copolymer (A-1) can further have structural units (C) other than the structural units (A1) to (A3) and the structural unit (B).
- At least a part of the structural unit of the copolymer (A-1) is a structural unit derived from a (meth) acrylic monomer.
- the ratio of the structural unit derived from the (meth) acrylic monomer to the total (100% by mass) of all the structural units in the copolymer (A-1) is preferably 20 to 100% by mass, and 40 to 100% by mass. Is more preferable.
- the structural unit (A1) has at least one structure (I) selected from the group consisting of structures represented by the following formula (1), the following formula (2), or the following formula (3).
- R 14 represents a hydrogen atom or an alkyl group
- R 1 and R 2 represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively.
- R 3 and R 5 each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group
- R 4 and R 6 each represents an alkylene group having 1 to 10 carbon atoms.
- X may be any of —O— (etheric oxygen atom), —S— (sulfide sulfur atom), and —NR 14 —, and is preferably —O—.
- examples of the alkyl group having 1 to 10 carbon atoms in R 1 and R 2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, 2- An ethylhexyl group etc. are mentioned.
- the number of carbon atoms of the alkyl group in R 1 and R 2 is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2.
- R 1 and R 2 include a combination of a hydrogen atom and a methyl group, a combination of a methyl group and a methyl group, a hydrogen atom and an alkyl group having 2 to 10 carbon atoms (hereinafter also referred to as “long-chain alkyl group”). .), A combination of a methyl group and a long chain alkyl group, a combination of a hydrogen atom and a hydrogen atom, a combination of a long chain alkyl group and a long chain alkyl group, and the like. Among these, a combination of a hydrogen atom and a methyl group is preferable in terms of hydrolyzability.
- Examples of the alkyl group having 1 to 20 carbon atoms in R 3 include the alkyl groups, decyl groups, dodecyl groups, and tetradecyl groups mentioned as the alkyl groups having 1 to 10 carbon atoms.
- the number of carbon atoms of the alkyl group in R 3 is preferably 1-10.
- the cycloalkyl group is preferably a cycloalkyl group having 4 to 8 carbon atoms, and examples thereof include a cyclohexyl group and a cyclopentyl group.
- As the aryl group an aryl group having 6 to 20 carbon atoms is preferable, and examples thereof include a phenyl group and a naphthyl group.
- R 3 is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group.
- the alkyl group, cycloalkyl group and aryl group in R 3 may each have a substituent selected from the group consisting of a cycloalkyl group, an aryl group, an alkoxy group, an alkanoyloxy group, an aralkyl group and an acetoxy group.
- the number of substituents may be one or two or more.
- Examples of the cycloalkyl group and aryl group as substituents are the same as those described above.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
- Examples of the alkanoyloxy group include an ethanoyloxy group.
- Examples of the aralkyl group include a benzyl group.
- examples of the alkylene group having 1 to 10 carbon atoms in R 4 include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.
- the alkylene group in R 4 preferably has 2 to 7 carbon atoms, and more preferably 3 to 4 carbon atoms.
- the alkylene group may be substituted with a substituent selected from the group consisting of a cycloalkyl group, an aryl group, an alkoxyl group, an alkanoyloxy group, an aralkyl group, and an acetoxy group. When substituted by a substituent, the number of substituents may be one or two or more. Specific examples of the substituent that may be substituted on the alkylene group include the same substituents as those for R 3 .
- R 5 is the same as R 3 in formula (1), and the preferred embodiment is also the same.
- R 6 is the same as R 4 in formula (2), and the preferred embodiment is also the same.
- the structural unit (A1) is typically a monomer (a1) unit having the structure (I).
- the monomer (a1) include monomers having the structure (I) and an ethylenically unsaturated bond (polymerizable carbon-carbon double bond).
- the monomer (a1) unit has a structure in which the ethylenically unsaturated bond of the monomer (a1) is cleaved to form a single bond.
- the monomer (a1) is preferably a monofunctional monomer having one ethylenically unsaturated bond from the viewpoint of lowering the viscosity when the copolymer (A-1) is dissolved in an organic solvent. .
- Examples of the monomer (a1) include a monomer represented by the following formula (a1-1), a monomer represented by the following formula (a1-2), and a monomer represented by the following formula (a1-3). And the like.
- R X represents the structure (I) or an alkyl ester group
- X represents —O—, —S— or —NR 14 —
- R 14 represents a hydrogen atom Or represents an alkyl group
- R 1 to R 6 are as defined above.
- CH 2 ⁇ CH—COO— is an acryloyloxy group
- CH 2 ⁇ C (CH 3 ) —COO— is a methacryloyloxy group.
- CH (CH 3 ) ⁇ CH—COO— is a crotonoyloxy group (ethylenically unsaturated bond is trans-type) or an isocrotonoyloxy group (ethylenically unsaturated bond is cis-type).
- CHR X CH-COO- is a maleoyloxy group (ethylenically unsaturated bond is cis type) or a fumaroyloxy group (ethylenic group) in which a carboxy group is substituted with a hemiacetal ester group, a hemiketal ester group or an alkyl ester group. Unsaturated bond is in trans form).
- the structure (I) in R X is the same as described above. When R X is the structure (I), R X preferably has the same structure as the group to which Z is bonded.
- R X is preferably a group represented by —CR 1 R 2 —XR 3 .
- R X1 represents an alkyl group.
- R X1 represents an alkyl group.
- an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.
- CH 2 ⁇ C (CH 2 R X ) —COO— or CH 2 ⁇ CR X —CH 2 COO— is an itaconoyloxy group in which a carboxy group is substituted with a hemiacetal ester group, a hemiketal ester group or an alkyl ester group It is.
- R X is the same as described above.
- Z is preferably CH 2 ⁇ CH—COO— or CH (CH 3 ) ⁇ CH—COO—.
- Examples of the monomer (a1) include those shown below.
- the monomer (a1) can be purchased as a commercial product, and can be appropriately synthesized using a known method.
- the monomer (a1) can be synthesized by converting the carboxy group of the monomer (a0) having a carboxy group into the structure (I).
- Examples of the monomer (a0) include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monomethyl fumarate, and the like.
- Examples of the method for converting the carboxy group of the monomer (a0) into the structure (I) include, for example, the monomer (a0), a compound represented by the following formula (11), and the following formula (12). Examples thereof include a method of reacting (addition reaction) a compound and at least one alkenyl compound selected from the group consisting of a compound represented by the following formula (13). You may use an alkenyl compound individually or in combination of 2 or more types.
- R 14 represents a hydrogen atom or an alkyl group
- R 7 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms
- R 8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 9 and R 11 each represents an alkyl group, a cycloalkyl group or an aryl group having 1 to 20 carbon atoms
- R 10 represents a single bond Or an alkylene group having 1 to 9 carbon atoms
- R 12 represents an alkylene group having 1 to 9 carbon atoms.
- Examples of the compound represented by the formula (11) include alkyl vinyl ethers (eg, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether), cycloalkyl vinyl ethers (eg, cyclohexyl vinyl ether) Vinyl ethers such as 1-propenyl ether such as ethyl-1-propenyl ether; 1-butenyl ethers such as ethyl-1-butenyl ether; and the like. Of these, vinyl ethers and 1-propenyl ethers are preferred.
- alkyl vinyl ethers eg, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether
- cycloalkyl vinyl ethers eg, cyclohexyl
- a compound in which R 4 in the formula (a1-2) is CH 2 —R 10 is obtained.
- the alkylene group having 1 to 9 carbon atoms in R 10 is the same as R 4 except that it has 9 or less carbon atoms.
- Examples of the compound represented by the formula (12) include dihydrofurans such as 2,3-dihydrofuran and 5-methyl-2,3-dihydrofuran; 3,4-dihydro-2H-pyran, 5,6 -Dihydropyrans such as dihydro-4-methoxy-2H-pyran; and the like.
- Examples of the compound represented by the formula (13) include 1-methoxy-1-cyclopentene, 1-methoxy-1-cyclohexene, 1-methoxy-1-cycloheptene, 1-ethoxy-1-cyclopentene, 1-ethoxy- 1-alkoxy-1-cycloalkylenes such as 1-cyclohexene, 1-butoxy-1-cyclopentene, 1-butoxy-1-cyclohexene; 1-alkoxy having substituents such as 1-ethoxy-3-methyl-1-cyclohexene -1-cycloalkylenes; and the like.
- the reaction between the monomer (a0) and the alkenyl compound proceeds under relatively mild conditions.
- the desired product can be obtained by carrying out the reaction for 5 to 10 hours while maintaining a reaction temperature of 40 to 100 ° C. in the presence or absence of an acidic catalyst such as hydrochloric acid, sulfuric acid or phosphoric acid.
- an acidic catalyst such as hydrochloric acid, sulfuric acid or phosphoric acid.
- the objective monomer can be recovered by distillation under reduced pressure under predetermined conditions.
- the structural unit (A2) has a triorganosilyloxycarbonyl group.
- the triorganosilyloxycarbonyl group include a group represented by the following formula (II). —CO—O—SiR 21 R 22 R 23 (II) (Wherein R 21 to R 23 each represents a hydrocarbon group having 1 to 20 carbon atoms)
- Examples of the hydrocarbon group in R 21 to R 23 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
- cycloalkyl group and the aryl group may have a substituent.
- substituents include a halogen atom, an alkyl group, an acyl group, a nitro group, and an amino group.
- the alkyl group as a substituent preferably has about 1 to 18 carbon atoms.
- R 21 to R 23 may be the same or different. It is preferable that at least one of R 21 to R 23 is an isopropyl group in that a coating film showing a stable polishing rate (polishing rate) can be obtained and the antifouling performance can be stably maintained for a long period of time.
- An isopropyl group is particularly preferred.
- the structural unit (A2) is typically a monomer (a2) unit having a triorganosilyloxycarbonyl group.
- the monomer (a2) include monomers having a triorganosilyloxycarbonyl group and an ethylenically unsaturated bond.
- the monomer (a2) is preferably a monofunctional monomer having one ethylenically unsaturated bond from the viewpoint of lowering the viscosity when the copolymer (A-1) is dissolved in an organic solvent. .
- Examples of the monomer (a2) include a monomer represented by the following formula (a2-1), a monomer represented by the following formula (a2-2), and the like. Among these, the monomer represented by the formula (a2-1) is preferable.
- CH 2 C (R 24 ) —CO—O—SiR 21 R 22 R 23 (a2-1)
- CH (COOR 25 ) C (R 24 ) —CO—O—SiR 21 R 22 R 23 (a2-2) (Wherein R 21 to R 23 are as defined above, R 24 represents a hydrogen atom or a methyl group, and R 25 represents an alkyl group.)
- Specific examples of the monomer represented by the formula (a2-1) include the following. Trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-n-hexylsilyl (Meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (Meth) acrylate, triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-s-butylsilyl
- examples of the alkyl group for R 25 include alkyl groups having 1 to 5 carbon atoms.
- Specific examples of the compound represented by the formula (a2-2) include the following. Triisopropylsilylmethyl malate, triisopropylsilylamyl malate, tri-n-butylsilyl-n-butylmalate, t-butyldiphenylsilylmethylmalate, t-butyldiphenylsilyl-n-butylmalate, triisopropylsilylmethyl fumarate, Triisopropylsilyl amyl fumarate, tri-n-butylsilyl-n-butyl fumarate, t-butyldiphenylsilylmethyl fumarate, t-butyldiphenylsilyl-n-butyl fumarate, etc.
- the monomer (a2) can be purchased as a commercial product, and can be appropriately synthesized using a known method.
- the structural unit (A3) has at least one structure (III) selected from the group consisting of structures represented by the following formula (4) or (5). -COO-M-OCO (4) -COO-MR 32 (5) (In the formula, M represents Zn, Cu, Mg or Ca, and R 32 represents an organic acid residue other than the (meth) acryloyloxy group.)
- the structural unit (A3) is typically a monomer (a3) unit having the structure (III).
- the structural unit (A3) and the monomer (a3) will be described in detail later.
- the structural units (A1) to (A3) are common in that they have a structure that can be hydrolyzed in seawater or the like.
- Monomers (a1) to (a3) are monomers not corresponding to the macromonomer (b).
- the structural unit (B) is a structural unit derived from the macromonomer (b).
- the macromonomer (b) is a compound having two or more structural units derived from a monomer having a radical polymerizable group and having a radical polymerizable group (hereinafter also referred to as “monomer (b1)”). Two or more structural units possessed by the macromonomer (b) may be the same or different.
- the radical polymerizable group possessed by the macromonomer (b) is preferably a group having an ethylenically unsaturated bond.
- the group having an ethylenically unsaturated bond include CH 2 ⁇ C (COOR) —CH 2 —, (meth) acryloyl group, 2- (hydroxymethyl) acryloyl group, vinyl group and the like.
- R represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted group.
- the heterocyclic group which has is shown.
- alkyl group in R examples include branched or straight chain alkyl groups having 1 to 20 carbon atoms. Specific examples of the branched or straight chain alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, and pentyl.
- the alicyclic group in R may be monocyclic or polycyclic, and examples thereof include alicyclic groups having 3 to 20 carbon atoms.
- the alicyclic group is preferably a saturated alicyclic group such as a cycloalkyl group, and specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a bicyclo [2.2.1].
- a heptyl group, a cyclooctyl group, an adamantyl group, etc. are mentioned.
- Examples of the aryl group in R include an aryl group having 6 to 18 carbon atoms.
- Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group and a naphthyl group.
- heterocyclic group in R examples include heterocyclic groups having 5 to 18 carbon atoms.
- Specific examples of the heterocyclic group having 5 to 18 carbon atoms include oxygen atom-containing heterocyclic groups such as ⁇ -butyrolactone group and ⁇ -caprolactone group, nitrogen atoms such as pyridyl group, carbazolyl group, pyrrolidinyl group, and pyrrolidone group.
- Examples thereof include a containing heterocyclic group and a morpholino group.
- the alkyl group, alicyclic group, aryl group, and heterocyclic group each may have a substituent.
- substituents include an alkyl group (except when R is an alkyl group having a substituent), an aryl group, —COOR 51 , a cyano group, —OR 52 , —NR 53 R 54 , —CONR 55 R 56 , at least one selected from the group consisting of a halogen atom, an allyl group, an epoxy group, a siloxy group, and a group exhibiting hydrophilicity or ionicity.
- R 51 to R 56 each independently represent a hydrogen atom, an alkyl group, an alicyclic group, or an aryl group. Each of these groups may be the same as described above.
- alkyl group and aryl group as the substituent include those similar to the alkyl group and aryl group in R, respectively.
- the R 51 in -COOR 51 in the substituent a hydrogen atom or an alkyl group. That is, —COOR 51 is preferably a carboxy group or an alkoxycarbonyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group.
- R 52 of —OR 52 in the substituent is preferably a hydrogen atom or an unsubstituted alkyl group. That is, —OR 52 is preferably a hydroxy group or an alkoxy group. Examples of the alkoxy group include an alkoxy group having 1 to 12 carbon atoms, and specific examples include a methoxy group.
- Examples of —NR 53 R 54 in the substituent include an amino group, a monomethylamino group, and a dimethylamino group.
- Examples of —CONR 55 R 56 in the substituent include a carbamoyl group (—CONH 2 ), an N-methylcarbamoyl group (—CONHCH 3 ), an N, N-dimethylcarbamoyl group (dimethylamide group: —CON (CH 3 ) 2 ) and the like.
- halogen atom in the said substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.
- hydrophilic or ionic group in the substituent include, for example, alkali salts of carboxy groups or alkali salts of sulfoxy groups, poly (alkylene oxide) groups such as polyethylene oxide groups and polypropylene oxide groups, and quaternary ammonium bases.
- alkali salts of carboxy groups or alkali salts of sulfoxy groups include, for example, alkali salts of carboxy groups or alkali salts of sulfoxy groups, poly (alkylene oxide) groups such as polyethylene oxide groups and polypropylene oxide groups, and quaternary ammonium bases.
- alkali salts of carboxy groups or alkali salts of sulfoxy groups include, for example, alkali salts of carboxy groups or alkali salts of s
- an alkyl group or a saturated alicyclic group is preferable, and an alkyl group or a saturated alicyclic group which is unsubstituted or has an alkyl group as a substituent is more preferable.
- methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl and octyl are preferred because of their availability.
- a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, isobornyl group and adamantyl group are preferred.
- the radically polymerizable group possessed by the monomer (b1) a group having an ethylenically unsaturated bond is preferred, similarly to the radically polymerizable group possessed by the macromonomer (b).
- the monomer (b1) various monomers can be used.
- Examples thereof include 4-methacryloyloxybenzophenone and (meth) acrylic acid-2-isocyanatoethyl. These monomers may be used individually by 1 type, and may use 2 or more types together. It is preferable that at least a part of the monomer (b1) is a (meth) acrylic monomer.
- structural unit (b ′) As the structural unit derived from the monomer (b1), a structural unit represented by the following formula (b ′) (hereinafter also referred to as “structural unit (b ′)”) is preferable. That is, the macromonomer (b) preferably has a radical polymerizable group and has two or more structural units (b ′).
- R 41 represents a hydrogen atom, a methyl group or CH 2 OH
- R 42 represents OR 43 , a halogen atom, COR 44 , COOR 45 , CN, CONR 46 R 47 or R 48.
- R 43 to R 47 each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted group; Having a heteroaryl group, an unsubstituted or substituted non-aromatic heterocyclic group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, or an unsubstituted or shows the organosilyl group having a substituent
- R 48 is an aryl group or an unsubstituted or substituted group having an unsubstituted or substituted het An
- Examples of the alkyl group, alicyclic group and aryl group in R 43 to R 47 are the same as the alkyl group, alicyclic group and aryl group in R described above.
- Examples of the heteroaryl group include a pyridyl group and a carbazolyl group.
- Examples of the non-aromatic heterocyclic group include a pyrrolidinyl group and a pyrrolidone group.
- Examples of the aralkyl group include a benzyl group and a phenylethyl group.
- Examples of the organosilyl group include a triorganosilyl group.
- Examples of the triorganosilyl group include a triorganosilyl group (for example, —SiR 21 R 22 R 23 ) in the triorganosilyloxycarbonyl group.
- the alkyl group, alicyclic group, aryl group, heteroaryl group, non-aromatic heterocyclic group, aralkyl group, alkaryl group, and organosilyl group each may have a substituent.
- substituents include carboxylic acid group (COOH), carboxylic acid ester group, epoxy group, hydroxy group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, isocyanato group, sulfonic acid group (SO 3 H), halogen atoms and the like.
- Examples of the carboxylic acid ester group include groups in which R 51 of —COOR 51 mentioned in the description of R is an alkyl group, an alicyclic group, or an aryl group.
- the alkoxy group, R 52 of the -OR 52 and the like groups are alkyl groups.
- Examples of the secondary amino group include groups in which R 53 of the —NR 53 R 54 is a hydrogen atom, and R 54 is an alkyl group, an alicyclic group, or an aryl group.
- Examples of the tertiary amino group include groups in which R 53 and R 54 of —NR 53 R 54 are each an alkyl group, an alicyclic group, or an aryl group.
- Examples of the alkyl group, aryl group, and halogen atom are the same as those described above.
- Examples of the aryl group and heteroaryl group for R 48 are the same as those described above.
- the aryl group and heteroaryl group each may have a substituent.
- Examples of the substituent include a carboxylic acid group, a carboxylic acid ester group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, a secondary amino group, a tertiary amino group, an isocyanato group, a sulfonic acid group, and a halogen atom. It is done.
- Examples of the carboxylic acid ester group, alkoxy group, primary amino group, secondary amino group, tertiary amino group, alkyl group, aryl group and halogen atom are the same as those described above.
- Examples of the olefin group include an allyl group.
- the olefin group may have a substituent. Examples of the substituent in the olefin group include those similar to the substituent in R 48.
- R 41 is a hydrogen atom or a methyl group and R 42 is COOR 45 is preferable.
- R 45 is preferably a hydrogen atom, an alkyl group, a saturated alicyclic group, an aryl group, a heteroaryl group or a non-aromatic heterocyclic group.
- the structural unit (b ′) is a structural unit derived from CH 2 ⁇ CR 41 R 42 .
- Substituted or unsubstituted alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 1-methyl-2-methoxyethyl ( Meth) acrylate, 3-methoxybutyl (meth) acrylate, 3-methyl-3-meth
- the macromonomer (b) may further have a structural unit other than the structural unit (b ′).
- Preferable specific examples of other structural units include structural units derived from the following monomers.
- the macromonomer (b) a macromonomer in which a radical polymerizable group is introduced at the end of the main chain containing two or more structural units (b ′) is preferable, and the macromonomer represented by the following formula (b-1) Is more preferable.
- R is as defined above, Q represents a main chain portion containing two or more structural units (b ′), and E represents a terminal group.
- R is the same as R in the aforementioned CH 2 ⁇ C (COOR) —CH 2 —, and the preferred embodiment is also the same.
- Two or more structural units (b ′) contained in Q may be the same or different.
- Q may consist of only the structural unit (b ′), or may further include another structural unit other than the structural unit (b ′).
- the number of structural units constituting Q is preferably such that the number average molecular weight of the macromonomer (b) falls within a preferred range described later.
- Examples of E include a hydrogen atom, a group derived from a radical polymerization initiator, a radical polymerizable group, and the like, similarly to a terminal group of a polymer obtained by known radical polymerization.
- a macromonomer represented by the following formula (b-2) is particularly preferable.
- R, R 41 , R 45 and E have the same meanings as described above, and n represents a natural number of 2 or more.
- n is a natural number of 2 or more. n is preferably in the range where the number average molecular weight (Mn) of the macromonomer (b) is 500 to 50,000. A more preferable range of the number average molecular weight is as follows.
- the n R 41 s may be the same or different.
- the n R 42 s may be the same or different.
- the number average molecular weight (Mn) of the macromonomer (b) is preferably from 500 to 50000, more preferably from 500 to less than 50000, further preferably from 800 to 30000, and particularly preferably from 1000 to 20000.
- the number average molecular weight of the macromonomer (b) is not less than the lower limit of the above range, the hardness and water resistance of the coating film are more excellent. If the number average molecular weight of the macromonomer (b) is not more than the upper limit of the above range, the storage stability of the copolymer (A-1) solution, the polymer-containing composition containing the copolymer (A-1), and the antifouling coating composition can be improved. Better.
- the number average molecular weight of the macromonomer (b) is measured by gel filtration chromatography (GPC) using polystyrene as a reference substance.
- the number average molecular weight of the macromonomer (b) can be adjusted by the amount of the polymerization initiator and the chain transfer agent used during the production of the macromonomer (b).
- the macromonomer (b) is preferably a macromonomer having two or more structural units (b ′) and a number average molecular weight (Mn) of 500 to 50,000.
- Mn number average molecular weight
- the preferred type of the structural unit (b ') in this macromonomer, and the more preferred number average molecular weight range are the same as described above.
- the glass transition temperature of the macromonomer (b) is preferably ⁇ 50 to 120 ° C., more preferably ⁇ 20 to 100 ° C., and further preferably 20 to 80 ° C. If the glass transition temperature of the macromonomer (b) is at least the lower limit of the above range, the hardness and water resistance of the coating film will be more excellent. If the glass transition temperature of the macromonomer (b) is not more than the upper limit of the above range, the solution of the copolymer (A-1) and the composition containing it (polymer-containing composition, antifouling coating composition) Storage stability is better. Moreover, it is easy to make those solutions and compositions have a low viscosity even at a high solid content.
- the glass transition temperature of the macromonomer (b) can be measured with a differential scanning calorimeter (DSC). The glass transition temperature of the macromonomer (b) can be adjusted by the composition of the monomer forming the macromonomer (b).
- the macromonomer (b) one produced by a known method may be used, or a commercially available one may be used.
- the method for producing the macromonomer (b) include a method using a cobalt chain transfer agent, a method using an ⁇ -substituted unsaturated compound such as ⁇ -methylstyrene dimer as a chain transfer agent, and a polymer having radical polymerizability. Examples thereof include a method of chemically bonding groups, a method by thermal decomposition, and the like.
- a method for producing the macromonomer (b) a method using a cobalt chain transfer agent is preferable because a catalyst having a small number of production steps and a high chain transfer constant is used.
- the macromonomer (b) produced using a cobalt chain transfer agent has a structure represented by the formula (b-1).
- Examples of the method for producing the macromonomer (b) using a cobalt chain transfer agent include a bulk polymerization method, a solution polymerization method, and an aqueous dispersion polymerization method such as a suspension polymerization method and an emulsion polymerization method.
- An aqueous dispersion polymerization method is preferred from the viewpoint that the recovery step is simple.
- As a method for chemically bonding a radical polymerizable group to a polymer for example, it is produced by substituting a halogen group of a polymer having a halogen group with a compound having a radical polymerizable carbon-carbon double bond.
- a method, a method of reacting a vinyl monomer having an acid group and a vinyl polymer having an epoxy group, a method of reacting a vinyl polymer having an epoxy group and a vinyl monomer having an acid group examples include a method of reacting a vinyl polymer having a hydroxyl group with a diisocyanate compound to obtain a vinyl polymer having an isocyanate group, and reacting this vinyl polymer with a vinyl monomer having a hydroxyl group. Any method may be used.
- the structural unit (C) is not particularly limited, and examples thereof include other monomers (c) other than the monomer (a1), the monomer (a2), the monomer (a3), and the macromonomer (b). ) Units.
- the monomer (c) is not particularly limited as long as it is copolymerizable with the monomer (a1), the monomer (a2), and the macromonomer (b), and is a radical such as an ethylenically unsaturated bond.
- Various monomers having a polymerizable group can be used.
- the same monomer (b1) for obtaining the macromonomer (b) mentioned above can be used (however, the monomer (a1), the monomer (a2) and the monomer ( excluding a3)).
- the monomer (c) can be used by appropriately selecting one or two or more as necessary.
- Monomer (c) is a monofunctional monomer having one ethylenically unsaturated bond from the viewpoint that when the copolymer (A-1) is dissolved in an organic solvent, it tends to have a low viscosity even at a high solid content. It is preferable that the ethylenically unsaturated bond is derived from an acryloyl group. That is, the monomer (c) is particularly preferably a monofunctional monomer having one acryloyl group.
- Monomer (c) is hydrophobic group-containing (meta) in that the flexibility, crack resistance and peel resistance of the coating film to be formed and long-term self-polishing properties can be improved in a good balance. It preferably contains an acrylate monomer.
- the hydrophobic group-containing (meth) acrylic acid ester monomer include substituted or unsubstituted alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate, behenyl (meth) acrylate, 1-methyl-2-
- the monomer (c) preferably contains an oxyethylene group-containing (meth) acrylic acid ester monomer from the viewpoint of the solubility and crack resistance of the coating film to be formed.
- an oxyethylene group-containing (meth) acrylic acid ester monomer a monomer represented by the following formula (c-1) is preferable.
- Z 1- (CH 2 CH 2 O) p R 57 (c-1) (In the formula, Z 1 represents a (meth) acryloyloxy group, R 57 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and p represents an integer of 1 to 15)
- p is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably an integer of 1 to 3, and particularly preferably 1 or 2.
- the monomer (c) preferably has no carboxy group from the viewpoint of the water resistance and the degree of wear of the coating film to be formed.
- the monomer (c) can be purchased as a commercial product, and can be appropriately synthesized using a known method.
- the total content of the structural unit (A1) and the structural unit (A2) in the copolymer (A-1) is the sum of all the structural units (100 mass). %) Is preferably 1 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass. When the total content of the structural unit (A1) and the structural unit (A2) is not less than the lower limit of the above range, the self-polishing property of the formed coating film is more excellent.
- the formed coating film has appropriate hydrolyzability, and self-polishing is maintained over a long period of time. In addition, the antifouling effect is more excellent.
- the content of the structural unit (B) in the copolymer (A-1) is preferably 1 to 60% by weight, more preferably 2 to 40% by weight, based on the total (100% by weight) of all the structural units. More preferably, it is ⁇ 30% by mass. If content of a structural unit (B) is more than the lower limit of the said range, the hardness and water resistance of the coating film formed will be more excellent. If the content of the structural unit (B) is not more than the upper limit of the above range, the solution viscosity when the copolymer (A-1) is dissolved in an organic solvent, and the polymer composition and antifouling paint containing this solution The viscosity of the composition is lower.
- the content of the structural unit (A3) in the copolymer (A-1) may be, for example, 0 to 97% by mass with respect to the total (100% by mass) of all the structural units.
- the content of the structural unit (C) is preferably 0 to 98% by mass, more preferably 5 to 88% by mass, and still more preferably 10 to 75% by mass with respect to the total (100% by mass) of all the structural units.
- the content of this structural unit is the sum of all the structural units in the copolymer (A-1).
- the content is preferably 1 to 90% by mass, and more preferably 10 to 80% by mass.
- the content of the structural unit is within the above range, the flexibility, crack resistance, and peel resistance of the coating film to be formed become higher and the antifouling effect becomes more excellent. If the content of this structural unit is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. Become.
- the content of this structural unit is the total structural unit in the copolymer (A-1).
- the amount is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 20 to 50% by mass.
- the content of the structural unit is not less than the lower limit of the above range, the hydrophilicity of the formed coating film becomes higher and the self-polishing property becomes more excellent. If the content of this structural unit is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. Become.
- the total of the structural unit (A1), the structural unit (A2), the structural unit (A3), the structural unit (B), and the structural unit (C) is 100% by mass.
- Content (mass%) of each structural unit in a copolymer can be measured by well-known methods, such as a gas chromatography, a high performance liquid chromatography, and a nuclear magnetic resonance spectrum method.
- Copolymer (A-1) is a monomer comprising at least one monomer (a ′) selected from the group consisting of monomer (a1) and monomer (a2) and macromonomer (b).
- a copolymer obtained by polymerizing a monomer mixture is preferred.
- a monomer mixture ( ⁇ 1) containing a monomer (a0) having an ethylenically unsaturated bond and a carboxy group and a macromonomer (b) is polymerized to have a carboxy group.
- the water resistance is more excellent.
- the monomer mixture is preferably composed of 1 to 80% by mass of monomer (a ′), 1 to 60% by mass of macromonomer (b), and 0 to 98% by mass of monomer (c). .
- the content of each monomer is a ratio with respect to the total amount of the monomer mixture.
- the range of the more preferable content of each monomer is the same as the range of the preferable content of the structural unit derived from each monomer.
- the weight average molecular weight (Mw) of the copolymer (A-1) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, still more preferably 5,000 to 30,000. 20,000 to 20,000 is particularly preferred. If the weight average molecular weight of the copolymer (A-1) is not more than the upper limit of the above range, the viscosity of the solution in which the copolymer (A-1) is dissolved in an organic solvent will be lower. It is easy to obtain a soil coating composition having a high solid content and a low viscosity. When the weight average molecular weight of the copolymer (A-1) is not less than the lower limit of the above range, the hardness, durability, etc. of the formed coating film are more excellent.
- the number average molecular weight (Mn) of the copolymer (A-1) is preferably 1,000 to 50,000, more preferably 2,000 to 25,000, still more preferably 2,500 to 15,000. , 10,000 to 10,000 are particularly preferred.
- the weight average molecular weight and the number average molecular weight are each measured by gel filtration chromatography (GPC) using polystyrene as a reference substance.
- the acid value of the copolymer (A-1) is preferably 5 mgKOH / g or less, more preferably 1 mgKOH / g or less, and may be 0 mgKOH / g. If the acid value of the copolymer (A-1) is not more than the above upper limit value, the water resistance of the formed coating film and the storage stability of the paint are more excellent. The acid value is measured by neutralization titration with a potassium hydroxide solution.
- the copolymer (A-1) is preferably a chain polymer having no cross-linked structure.
- the viscosity of a solution obtained by dissolving the copolymer (A-1) in an organic solvent is lower than that in the case of having a crosslinked structure.
- Method for producing copolymer (A-1) examples include the following production method ( ⁇ ).
- the monomer mixture ( ⁇ 1) may further include a monomer (a3) and another monomer (c).
- the copolymer (A-1) can also be produced by the following production method ( ⁇ ).
- the monomer mixture ( ⁇ 1) may further contain a monomer (a2), a monomer (a3), and another monomer (c).
- the composition of the monomer mixture ( ⁇ 1) that is, the type of monomer constituting the monomer mixture ( ⁇ 1) and the content of each monomer relative to the total mass of all monomers ( % By mass) is the composition of the copolymer (A-1), that is, the type of the structural unit derived from each monomer constituting the copolymer (A-1) and the total mass of all the structural units. This is the same as the content (% by mass).
- the polymerization of the monomer mixture ( ⁇ 1) can be carried out in the same manner as the polymerization of the monomer mixture in the method for producing the (meth) acrylic copolymer of the sixth aspect described later.
- the composition of the monomer mixture ( ⁇ 1) is the same as that of the copolymer (A-1) except that the monomer (a1) is the monomer (a0). .
- the monomer (a0) is the same as that described in the description of the monomer (a1).
- the polymerization of the monomer mixture ( ⁇ 1) can be performed in the same manner as the polymerization of the monomer mixture ( ⁇ 1) in the production method ( ⁇ ).
- Examples of the method for converting the carboxy group of the copolymer (A0) into the structure (I) include the copolymer (A0), the compound represented by the formula (11), and the formula (12). And a method of reacting (addition reaction) with at least one alkenyl compound selected from the group consisting of the compound represented by formula (13). Examples of the alkenyl compound are the same as those described above.
- the reaction between the copolymer (A0) and 1-alkenyl ether can be carried out in the same manner as the reaction between the monomer (a0) and the alkenyl compound.
- the copolymer (A-1) Since the copolymer (A-1) has at least one structural unit selected from the group consisting of the structural unit (A1) and the structural unit (A2), it can be hydrolyzed in seawater or the like. Therefore, the coating film containing the copolymer (A-1) exhibits self-polishing properties in seawater or the like. That is, the copolymer (A-1) has one or both of the structure (I) and the triorganosilyloxycarbonyl group. In this state, the copolymer (A-1) does not dissolve in seawater. When (I) or a triorganosilyloxycarbonyl group is hydrolyzed, a carboxy group or the like is generated and dissolved in seawater.
- the coating surface gradually dissolves in seawater and is renewed (self-polishing). Therefore, the coating film of the antifouling coating composition containing the copolymer (A-1) also exhibits self-polishing properties. This coating film is renewed in seawater and exhibits antifouling properties. In particular, when the coating film contains an antifouling agent, the antifouling agent is always exposed on the surface of the coating film, and an excellent antifouling effect is exhibited over a long period of time.
- the copolymer (A-1) has at least one structural unit selected from the group consisting of the structural unit (A1) and the structural unit (A2) and the structural unit (B).
- a coating film having excellent properties and hardness can be formed. Furthermore, this coating film can be made excellent in the degree of wear and the adhesion to the substrate. Such a coating film is unlikely to cause damage or peeling of the coating film, which causes a decrease in the antifouling effect, or a decrease in the degree of wear over time. Therefore, it is excellent in static antifouling property in seawater or the like, and the antifouling effect is stably exhibited over a long period of time.
- the copolymer (A-1) has at least one structural unit selected from the group consisting of the structural unit (A1) and the structural unit (A2) and the structural unit (B).
- a polymer-containing composition containing the copolymer (A-1) and an organic solvent can be made into a solution having a high solid content and a low viscosity, and is excellent in storage stability. If the polymer-containing composition has a high solid content and a low viscosity, an antifouling coating composition having coating suitability can be obtained without adding an organic solvent during the production of the antifouling coating composition. Further, when an antifouling agent or the like is added, it can be mixed well with the antifouling agent or the like without adding an organic solvent.
- an antifouling coating composition having a low VOC content for example, 430 g / L or less
- a low VOC content for example, 430 g / L or less
- the hardness of the coating film tends to decrease.
- the copolymer (A-1) in the antifouling coating composition a coating film having excellent hardness can be formed even when the antifouling coating composition has a high solid content and a low viscosity.
- the rate of increase in the hardness of the coating film immediately after coating is high.
- the copolymer (A-1) is suitable for an antifouling coating composition.
- the use of the copolymer (A-1) is not limited to the antifouling coating composition, and can be used for other uses such as an antifogging coating composition.
- a second aspect of the present invention is a (meth) acrylic copolymer (hereinafter also referred to as “copolymer (A-2)”) having a structural unit (A3) and a structural unit (B). And a solvent having a viscosity at 25 ° C. of 5 ⁇ 10 4 mPa ⁇ s or less.
- the polymer is dissolved in the organic solvent.
- the copolymer (A-2) can further have a structural unit (A1), a structural unit (A2), and a structural unit (C).
- the structural unit (B), the structural unit (A1), the structural unit (A2), and the structural unit (C) are the same as described above.
- At least a part of the structural unit of the copolymer (A-2) is a structural unit derived from a (meth) acrylic monomer.
- the ratio of the structural unit derived from the (meth) acrylic monomer to the total (100% by mass) of all the structural units in the copolymer (A-2) is preferably 20 to 100% by mass, and 40 to 100% by mass. Is more preferable.
- the structural unit (A3) has at least one structure (III) selected from the group consisting of structures represented by the following formula (4) or (5). -COO-M-OCO (4) -COO-MR 32 (5) (In the formula, M represents Zn, Cu, Mg or Ca, and R 32 represents an organic acid residue other than the (meth) acryloyloxy group.)
- the organic acid residue of R 32 refers to the remaining part obtained by removing one proton from the organic acid (for example, the remaining part obtained by removing the proton from the carboxy group of the carboxylic acid), and ion-bonded to M instead of this proton. ing.
- a carboxylic acid is preferable. 1,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylic acid, pyruvic acid, naphthenic acid, abietic acid, hydrogenated abietic acid and other monocarboxylic acids Etc.
- R 32 is preferably a fatty acid residue having 1 to 20 carbon atoms (aliphatic monocarboxylic acid residue) from the viewpoint of obtaining a highly durable coating film that can prevent cracking and peeling over a long period of time.
- the structural unit (A3) is typically a monomer (a3) unit having the structure (III).
- the monomer (a3) having the structure (III) for example, a monomer in which a vinyl group having an unsubstituted or substituted group is bonded to both ends of the group represented by the formula (4), the formula (5) ), A monomer having an unsubstituted or substituted vinyl group bonded to one end (the side opposite to the R 32 side).
- Examples of the monomer having the vinyl group bonded to both ends of the group represented by the formula (4) include, for example, a monomer represented by the following formula (a3-1) (hereinafter referred to as “monomer (a3-1)”. ) ").).
- a monomer represented by the following formula (a3-2) hereinafter referred to as “monomer (a3-2) ) ").
- M represents Zn, Cu, Mg or Ca
- R 31 represents a hydrogen atom or a methyl group
- R 32 represents an organic acid residue other than a (meth) acryloyloxy group.
- M and R 32 are the same as described above, and the preferred embodiments are also the same.
- any one of these may be used alone, or two or more may be used in combination.
- zinc (meth) acrylate and copper (meth) acrylate are preferred because the transparency of the copolymer (A-2) tends to be high and the color tone of the coating film containing the copolymer (A-2) tends to be beautiful.
- Examples of the monomer (a3-2) include monochloro magnesium acetate (meth) acrylate, monochloro calcium acetate (meth) acrylate, monochloro zinc acetate (meth) acrylate, monochloro copper acetate (meth) acrylate; monofluoro magnesium acetate (meta) ) Acrylate, calcium monofluoroacetate (meth) acrylate, zinc monofluoroacetate (meth) acrylate, copper monofluoroacetate (meth) acrylate; magnesium acetate (meth) acrylate, calcium acetate (meth) acrylate, zinc acetate (meth) acrylate , Copper acetate (meth) acrylate; magnesium propionate (meth) acrylate, calcium propionate (meth) acrylate, zinc propionate (meth) acrylate, copper propionate (meta Acrylate; magnesium octylate (meth) acrylate, calcium octy
- a zinc-containing monomer in which M is Zn is preferable because the transparency of the copolymer (A-2) tends to be high and the color tone of the coating film containing the copolymer (A-2) tends to be beautiful. Furthermore, from the viewpoint of durability of the resulting coating film, fatty acid zinc (meth) acrylate (M in formula (a3-2) is Zn, R 22 is a fatty acid residue), or fatty acid copper (meth) acrylate (In the formula (a3-2), M is Cu and R 22 is a fatty acid residue) is more preferable.
- Monomer (a3) is a monomer (a3-1) and monomer (a3-2) from the viewpoint that the self-polishing property of the resulting coating film is maintained over a long period of time and good antifouling properties are obtained. Both can be included. That is, the copolymer (A-2) can have both a monomer (a3-1) unit and a monomer (a3-2) unit.
- the monomer (a3-1) and the monomer (a3-2) a combination of zinc (meth) acrylate and fatty acid zinc (meth) acrylate, or (meth) acrylic acid copper and fatty acid copper (Meth) acrylate is preferred.
- Monomer (a3) one produced by a known method may be used, or a commercially available one may be used.
- Monomer (a3-1) is, for example, an inorganic metal compound containing a metal element corresponding to M in formula (a3-1) and (meth) acrylic acid, a diluent such as an organic solvent, or ethylenic It is obtained by a method of reacting in a reactive diluent having a polymerizable unsaturated group such as an unsaturated monomer.
- the mixture containing the metal-containing polymerizable monomer obtained by this method is excellent in compatibility with organic solvents and other monomers, and can be easily polymerized.
- the reaction is preferably performed in the presence of water, and the water content in the reaction product is preferably in the range of 0.01 to 30% by mass.
- the inorganic metal compound include oxides, hydroxides and chlorides of metals selected from Zn, Cu, Mg and Ca.
- Monomer (a3-2) includes, for example, an inorganic metal compound containing a metal element corresponding to M in formula (a3-2), (meth) acrylic acid, and an organic acid residue in formula (32) and an organic acid corresponding to R 32, obtainable by a method of reacting in a reactive diluent having a polymerizable unsaturated group such as a diluent or ethylenically unsaturated monomers such as an organic solvent.
- the inorganic metal compound include those similar to the inorganic metal compound for obtaining the monomer (a3-1).
- the monomer mixture containing the monomer (a3-1) and the monomer (a3-2) is, for example, a metal element corresponding to M in the formulas (a3-1) to (a3-2). and inorganic metal compounds containing, (meth) acrylic acid, wherein the organic acid corresponding to the organic acid residue R 32 in (a3-2), a diluent such as an organic solvent or ethylenically unsaturated monomers such as It can be obtained by a method of reacting in a reactive diluent.
- the amount of the organic acid corresponding to R 22 is preferably 0.01 to 3 times mol, more preferably 0.01 to 0.95 times mol, and 0.1 More preferably, the molar ratio is ⁇ 0.7 times.
- the content of the organic acid is 0.01 times mol or more, solid precipitation is suppressed in the production process of the monomer mixture, and self-polishing properties and crack resistance of the obtained coating film are better. It becomes.
- the amount is 3 times or less, the antifouling property of the resulting coating film tends to be maintained for a longer period.
- the content of the structural unit (A3) in the copolymer (A-2) is preferably 1 to 40% by weight and more preferably 5 to 30% by weight with respect to the total (100% by weight) of all the structural units. If content of a structural unit (A3) is more than the lower limit of the said range, the self-polishing property of the coating film formed will be more excellent. If the content of the structural unit (A3) is less than or equal to the upper limit of the above range, the storage stability of the polymer solution, the polymer composition containing it, the antifouling coating composition, etc., and the adhesion of the coating film to be formed The water resistance in seawater and the balance between hardness and crack resistance tend to be improved.
- the content of the structural unit (B) in the copolymer (A-2) is preferably 1 to 60% by weight, more preferably 2 to 40% by weight, based on the total of all the structural units (100% by weight). More preferably, it is ⁇ 30% by mass. If content of a structural unit (B) is more than the lower limit of the said range, the hardness of the coating film formed, the water resistance in seawater, and adhesiveness will be more excellent. Moreover, even if a polymer solution, a polymer composition containing the same, and an antifouling coating composition have a high solid content, the viscosity can be lowered.
- the content of the structural unit (B) is not more than the upper limit of the above range, the cracking property of the coating film to be formed, the storage stability of the polymer solution, the polymer composition containing it, the antifouling paint composition, etc. Is better.
- the total content of the structural unit (A1) and the structural unit (A2) in the copolymer (A-2) is, for example, 0 to 30% by mass with respect to the total (100% by mass) of all the structural units. Good.
- the content of the structural unit (C) is preferably 10 to 98% by mass with respect to the total (100% by mass) of all the structural units, More preferably, it is -93 mass%, and 30-90 mass% is further more preferable.
- the content of the structural unit derived from the carboxy group-containing unsaturated monomer is preferably 10% by mass or less, preferably 5% by mass with respect to the total (100% by mass) of all the structural units. % Or less is more preferable, and 0% by mass is particularly preferable. That is, it is particularly preferable that the copolymer (A-2) does not contain a structural unit derived from a carboxy group-containing unsaturated monomer.
- the content of the structural unit derived from the carboxy group-containing unsaturated monomer is not more than the above upper limit, the water resistance of the coating film to be formed, the polymer solution, the polymer-containing composition containing this, and the antifouling paint
- the storage stability of the composition and the like is more excellent, and the antifouling coating composition tends to have a low viscosity even at a high solid content.
- the copolymer (A-2) is preferably a copolymer obtained by polymerizing a monomer mixture containing the monomer (a3) and the macromonomer (b). With such a copolymer, a monomer mixture containing a monomer having an ethylenically unsaturated bond and a carboxy group and a macromonomer is polymerized to obtain a copolymer having a carboxy group. Compared to a copolymer obtained by converting the carboxy group of the copolymer into the structure (III), the water resistance is more excellent.
- the monomer mixture is preferably composed of 1 to 40% by mass of monomer (a3), 1 to 60% by mass of macromonomer (b), and 10 to 98% by mass of monomer (c).
- the content of each monomer is a ratio with respect to the total amount of the monomer mixture.
- the range of the more preferable content of each monomer is the same as the range of the preferable content of the structural unit derived from each monomer.
- the weight average molecular weight (Mw) of the copolymer (A-2) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and further preferably 4,000 to 20,000.
- the weight average molecular weight of the copolymer (A-2) is not more than the upper limit of the above range, the hardness of the coating film is more excellent.
- the antifouling property of the coating film formed is excellent.
- the weight average molecular weight of the copolymer (A-2) is not less than the lower limit of the above range, the hardness and durability of the coating film to be formed are more excellent.
- the number average molecular weight (Mn) of the copolymer (A-2) is preferably 1,000 to 50,000, more preferably 2,000 to 25,000.
- the polydispersity (Mw / Mn) of the copolymer (A-2) is preferably 1.5 to 5.0, more preferably 2.2 to 3.0.
- the acid value of the copolymer (A-2) is preferably 1 to 140 mgKOH / g, more preferably 5 to 130 mgKOH / g, and still more preferably 10 to 120 mgKOH / g. If the acid value of a copolymer (A) is below the upper limit of the said range, the water resistance of a coating film and crack resistance will be more excellent.
- the acid value of the copolymer (A-2) is measured by a known method such as neutralization titration with a potassium hydroxide solution.
- the copolymer (A-2) contained in the polymer solution of this embodiment may be one type or two or more types.
- the content of the copolymer (A-2) in the polymer solution of this embodiment is preferably 85% by mass or less, more preferably 10 to 80% by mass, and more preferably 30 to 30% by mass with respect to the total amount of the polymer solution. 75% by mass is more preferable, and 55 to 75% by mass is particularly preferable. If the content of the copolymer (A-2) is not more than the above upper limit value, a coating film excellent in water resistance, coating film hardness, etc. tends to be obtained. When the content of the copolymer (A-2) is not less than the lower limit, an antifouling coating composition having a low VOC content can be easily obtained.
- the organic solvent is not particularly limited as long as it can dissolve the copolymer (A-2).
- monohydric alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol; ethylene glycol, 1,2-propylene Polyhydric alcohol solvents such as glycol; Ketone solvents such as acetone, methyl ethyl ketone, acetyl acetone, and methyl isobutyl ketone; Ether solvents such as methyl ethyl ether and dioxane; Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol mono n-propyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropiate Glycol ether solvents such as ethylene glycol monopropyl ether; glycol acetate solvents such as
- the content of the organic solvent in the polymer solution of this embodiment is not particularly limited as long as the viscosity at 25 ° C. of the polymer solution is 5 ⁇ 10 4 mPa ⁇ s or less.
- the polymer solution It is 30% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and 100% by mass with respect to the total amount excluding the copolymer (A-2) from the solution. It may be. If content of an organic solvent is more than the said lower limit, it will be easy to obtain the coating film which was excellent in water resistance and excellent in drying property. When the content of the organic solvent is not more than the above upper limit value, an antifouling coating composition having a low VOC content can be easily obtained.
- the polymer solution of this embodiment may further contain other components other than the copolymer (A-2) and the organic solvent.
- the other components include the same components as the other components in the antifouling coating composition described later.
- the content of other components is preferably 200% by mass or less, and may be 0% by mass with respect to the copolymer (A-2) (100% by mass).
- the viscosity at 25 ° C. of the polymer solution of this embodiment is 5 ⁇ 10 4 mPa ⁇ s or less, preferably 5000 mPa ⁇ s or less, more preferably less than 5000 mPa ⁇ s, still more preferably less than 4000 mPa ⁇ s, and more preferably 3000 mPa ⁇ s. Is more preferably less than 2,000 mPa ⁇ s, particularly preferably less than 1,000 mPa ⁇ s.
- the polymer solution of this embodiment preferably has a viscosity at least at a solid content of 55% by mass not more than the above preferred upper limit.
- the minimum of the viscosity of a polymer solution is not specifically limited, 100 mPa * s or more is preferable at the point of the coating sagging suppression at the time of coating. Accordingly, the viscosity of the polymer solution at 25 ° C.
- ⁇ ⁇ s is preferably 100 to 5 ⁇ 10 4 mPa ⁇ s, more preferably 100 to 5000 mPa ⁇ s, still more preferably 100 mPa ⁇ s to less than 5,000 mPa ⁇ s, and 100 mPa ⁇ s. More preferably less than 4,000 mPa ⁇ s, more preferably more than 100 mPa ⁇ s and less than 3,000 mPa ⁇ s, further preferably more than 100 mPa ⁇ s and less than 2,000 mPa ⁇ s, more preferably more than 100 mPa ⁇ s and less than 1,000 mPa ⁇ s. Particularly preferred.
- the viscosity of the polymer solution is the solid content of the polymer solution (contents of the copolymer (A-2) and other components), the weight average molecular weight of the copolymer (A-2), the glass transition temperature, the crosslinked structure. It can be adjusted by the presence or absence of. For example, the lower the solid content, particularly the content of the copolymer (A-2), the lower the viscosity. In addition, the smaller the weight average molecular weight of the copolymer (A-2) or the lower the glass transition temperature, the lower the viscosity.
- the ratio (VX) obtained by the following formula (i) is preferably 20 or less, more preferably 17 or less, and still more preferably 10 or less.
- Ratio (VX) viscosity (VB) / solid content (NV) (i)
- Viscosity (VB) indicates the viscosity (mPa ⁇ s) measured with a B-type viscometer at 25 ° C. of the sample (polymer solution), and solid content (NV) indicates the heating residue (mass%) of the sample. .
- the ratio (VX) is 10.
- the solid content (heating residue) of the sample is measured by the method described in Examples described later. If the ratio (VX) is less than or equal to the above upper limit value, an antifouling agent or the like is blended or coated without adding an organic solvent for dilution to the polymer solution or the polymer composition containing the polymer solution. Thus, an antifouling coating composition having a low VOC content can be obtained.
- Examples of the method for producing the polymer solution of this embodiment include a method of producing the copolymer (A-2) by the following production method ( ⁇ ) or ( ⁇ ), and adding an organic solvent as necessary. It is done. Among these, from the viewpoint of water resistance, a method of producing the copolymer (A-2) by the production method ( ⁇ ) and adding an organic solvent as necessary is preferable.
- the monomer mixture ( ⁇ 1) may further include a monomer (a1), a monomer (a2), and a monomer (c).
- the composition of the monomer mixture ( ⁇ 1) is the same as that of the copolymer (A-2).
- the polymerization of the monomer mixture ( ⁇ 1) can be performed in the same manner as the polymerization of the monomer mixture in the method for producing a (meth) acrylic copolymer according to the sixth aspect described later.
- the polymerization product obtained by polymerization of the monomer mixture ( ⁇ 1) contains an organic solvent and the viscosity at 25 ° C. is not more than the above upper limit, the polymerization product is used as it is with the polymer solution of this embodiment. can do.
- An additional organic solvent may be added in order to reduce viscosity, improve handling properties, and the like.
- the polymerization product or the copolymer (A-2) recovered from the polymerization product is added to the organic product.
- a solvent is added to obtain the polymer solution of this embodiment.
- the monomer mixture ( ⁇ 1) may further include a monomer (a1), a monomer (a2), and a monomer (c).
- the composition of the monomer mixture ( ⁇ 1) is the same as that of the copolymer (A-2) except that the monomer (a3) is the monomer (a0).
- the polymerization of the monomer mixture ( ⁇ 1) can be carried out in the same manner as the polymerization of the monomer mixture in the method for producing the (meth) acrylic copolymer of the sixth aspect described later.
- the reaction between the copolymer (A0 ′) and the organic acid metal salt is carried out, for example, by raising the temperature to the reflux temperature and removing the mixed liquid of organic acid such as acetic acid such as acetic acid, water, and organic solvent, and the same amount of organic The reaction can be carried out by continuing the reaction for 10 to 20 hours while replenishing the solvent.
- Production method ( ⁇ ) polymerization of a monomer mixture ( ⁇ 1) containing the monomer (a3) and the macromonomer (b) in an organic solvent, and as a polymerization product or a polymerization product obtained by the polymerization A method of obtaining a polymer solution of this embodiment by diluting a product with an organic solvent.
- the monomer mixture ( ⁇ 1) may further include a monomer (a1), a monomer (a2), and a monomer (c).
- the composition of the monomer mixture ( ⁇ 1) is the same as that of the copolymer (A-2).
- the method for producing the (meth) acrylic copolymer according to the sixth aspect described later except that the polymerization of the monomer mixture ( ⁇ 1) is essential to be performed in an organic solvent (that is, performed by a solution polymerization method).
- the polymerization can be carried out in the same manner as in the polymerization of the monomer mixture.
- organic solvent used for copolymerization or dilution a general organic solvent can be used, and examples thereof include the same organic solvents listed as the organic solvent for the polymer solution.
- the organic solvent used for copolymerization and the organic solvent used for dilution may be the same or different.
- the preferable range of the ratio of the organic solvent to the total amount excluding all monomers from the reaction system is the preferable range of the content of the organic solvent to the total amount excluding the copolymer (A-2) from the polymer solution. It is the same.
- the entire reaction system is the total of all materials used for copolymerization (various monomers, organic solvents, radical polymerization initiators and chain transfer agents used as necessary).
- the copolymerization may be carried out in an organic solvent of 30% by mass or more based on the total amount excluding all monomers from the entire reaction system. It may be performed in an organic solvent of less than 30% by mass.
- the ratio of the organic solvent with respect to the total amount excluding all monomers from the reaction system is lower than the content of the organic solvent with respect to the total amount excluding the copolymer (A-2) from the polymer solution.
- the lower limit of the ratio of the organic solvent to the total amount excluding all monomers from the reaction system is not particularly limited, but 20% by mass or more is preferable because the lower the solution viscosity during polymerization, the better the polymerization stability.
- the copolymer (A-2) Since the copolymer (A-2) has the structural unit (A3), it can be hydrolyzed in seawater or the like. Therefore, the coating film containing the copolymer (A-2) exhibits self-polishing properties in seawater. That is, the copolymer (A-2) has one or both of a —CO—O—M—O—CO— structure and a —CO—O—M—R 32 structure. Although it does not dissolve in seawater, when this structure is hydrolyzed by contact with seawater, a carboxy group or the like is generated and dissolved in seawater. The coating surface gradually dissolves in seawater and is renewed (self-polishing).
- the polymer-containing composition containing the polymer solution of this embodiment and the coating film of the antifouling coating composition containing the same also exhibit self-polishing properties.
- This coating film is renewed in seawater and exhibits antifouling properties.
- the coating film contains an antifouling agent, the antifouling agent is always exposed on the surface of the coating film, and an excellent antifouling effect is exhibited over a long period of time.
- the polymer solution of this embodiment includes the copolymer (A-2) having the structural unit (A3) and the structural unit (B), and has a viscosity of 5 ⁇ 10 4 mPa ⁇ s or less. Therefore, the formed coating film is excellent in water resistance and hardness. Therefore, the coating film is less likely to be damaged or peeled, which causes a decrease in the antifouling effect. Further, the dissolution rate (consumption level) of the coating film in seawater or the like is sufficiently high. Therefore, it is excellent in stationary antifouling property in seawater and the like, and an excellent antifouling effect is stably exhibited over a long period of time.
- the polymer solution and the polymer-containing composition containing the polymer solution can be made into a solution with a high solid content and a low viscosity. If the polymer-containing composition has a high solid content and a low viscosity, an antifouling coating composition having coating suitability can be obtained without adding an organic solvent during the production of the antifouling coating composition. Further, when an antifouling agent or the like is added, it can be mixed well with the antifouling agent or the like without adding an organic solvent. Therefore, an antifouling paint composition having a low VOC content (for example, 500 g / L or less) can be obtained.
- a low VOC content for example, 500 g / L or less
- an antifouling coating composition when intended to have a high solid content and a low viscosity, the hardness of the coating film tends to decrease.
- the polymer solution of this embodiment for the antifouling coating composition, even when the antifouling coating composition has a high solid content and a low viscosity, a coating film having excellent hardness can be formed.
- the rate of increase in the hardness of the coating film immediately after coating is high, and the resistance to cracking is high. Tend. When this rate of increase is slow, it takes time for the hardness of the coating film to be sufficiently high.
- the coated material is moved before the hardness of the coating film becomes sufficiently high, the coating film is deformed and the appearance and the like are deteriorated, so that it takes time to proceed to the next step after coating.
- a high rate of increase in the hardness of the coating film is preferable in terms of productivity.
- the polymer solution of this embodiment is suitable for an antifouling coating composition.
- the use of the polymer solution of the present embodiment is not limited to the antifouling coating composition, and can be used for other uses such as an antifogging coating composition.
- composition (B-1) The third aspect of the present invention is a polymer-containing composition (hereinafter also referred to as “composition (B-1)”) comprising the copolymer (A-1) of the first aspect.
- composition (B-2) a polymer-containing composition (hereinafter also referred to as “composition (B-2)”) comprising the polymer solution of the second aspect.
- the copolymer (A-1) contained in the composition (B-1) may be one type or two or more types.
- the content of the copolymer (A-1) in the composition (B-1) is preferably 50% by mass or more, more preferably 57% by mass or more, based on the total mass of the composition (B-1). 59 mass% or more is more preferable. If the content of the copolymer (A-1) is not less than the lower limit, the content of the organic solvent that can be contained in the composition (B-1) is relatively reduced, and the content of the VOC is low. A dirty paint composition can be easily obtained.
- the upper limit of the content of the copolymer (A-1) is not particularly limited, and may be 100% by mass.
- the viscosity of the composition (B-1) at 25 ° C. is 5 ⁇ 10 4 or less, and the weight average of the copolymer (A-1) although it varies depending on the molecular weight, glass transition temperature, presence or absence of a crosslinked structure, etc., it is preferably 80% by mass or less, more preferably 85% by mass or less.
- the composition (B-1) preferably further contains an organic solvent.
- the organic solvent is not particularly limited as long as it can dissolve the copolymer (A-1).
- hydrocarbon solvents such as toluene and xylene
- ether solvents such as 1-alkenyl ether
- methyl isobutyl ketone and the like Ketone solvents for example, hydrocarbon solvents such as toluene and xylene
- ether solvents such as 1-alkenyl ether
- ester solvents such as n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate; and the like. Any of these may be used alone or in combinations of two or more.
- the composition (B-1) contains, as an organic solvent, the compound represented by the formula (11), the formula It is preferable to include at least one alkenyl compound selected from the group consisting of the compound represented by (12) and the compound represented by the formula (13).
- the alkenyl compound By including the alkenyl compound in the composition (B-1), the storage stability of the composition (B-1) and the antifouling coating composition containing the composition is improved. Examples of the alkenyl compound are the same as those described above.
- An alkenyl compound can be used individually by 1 type or in combination of 2 or more types.
- vinyl ethers such as butyl vinyl ether and isobutyl vinyl ether are preferable in that the effect of improving storage stability is more excellent.
- 1-alkenyl ether and other organic solvent may be used in combination.
- the content of the alkenyl compound is preferably 20 mol% or more, more preferably 30 to 1000 mol%, and further preferably 40 to 800 mol% with respect to the structure (I) of the copolymer (A-1). preferable. If content of an alkenyl compound is in the said range, the improvement effect of storage stability will be more excellent.
- the content of the organic solvent in the composition (B-1) is preferably 43% by mass or less, more preferably 41% by mass or less, and further preferably 39% by mass or less with respect to the total mass of the composition (B-1). preferable.
- the content of the organic solvent is preferably such that the viscosity of the composition (B-1) at 25 ° C. is 5 ⁇ 10 4 or less, and the weight average molecular weight, glass transition temperature, crosslinked structure of the copolymer (A-1) Although it varies depending on the presence or absence, etc., it is preferably 30% by mass or more, more preferably 25% by mass or more.
- the composition (B-1) may further contain components other than the copolymer (A-1) and the organic solvent.
- the other components include the same components as the other components in the antifouling coating composition described later.
- the content of other components is preferably 300% by mass or less, and may be 0% by mass with respect to copolymer (A-1) (100% by mass).
- the viscosity of the composition (B-1) at 25 ° C. is preferably 5 ⁇ 10 4 mPa ⁇ s or less. A more preferable viscosity is the same as the viscosity at 25 ° C. of the polymer solution of the second embodiment.
- the composition (B-1) preferably has a viscosity at least at a solid content of 55% by mass not more than the preferable upper limit.
- the viscosity of the composition (B-1) measured by a Gardner bubble viscometer is preferably W or less, more preferably V or less, and even more preferably U or less. If the viscosity of the composition (B-1) is not more than the above upper limit value, an antifouling agent or the like is added to or painted on the composition (B-1) without adding an organic solvent for dilution. And an antifouling coating composition having a low VOC content is obtained.
- the lower limit of the viscosity is not particularly limited.
- the viscosity of the composition (B-1) depends on the solid content of the composition (B-1) (contents of the copolymer (A-1) and other components) and the weight average of the copolymer (A-1). It can be adjusted by the molecular weight, glass transition temperature, presence or absence of a crosslinked structure, and the like. For example, the lower the solid content, particularly the content of the copolymer (A-1), the lower the viscosity. In addition, the smaller the weight average molecular weight of the copolymer (A-1) or the lower the glass transition temperature, the lower the viscosity.
- the ratio (VX) obtained by the formula (i) is preferably 20 or less, more preferably 17 or less, and still more preferably 10 or less. If the ratio (VX) is less than or equal to the above upper limit value, an antifouling agent or the like can be blended or applied to the composition (B-1) without adding an organic solvent for dilution. An antifouling coating composition having a low content is obtained.
- the ratio (VX) is calculated by substituting the viscosity and solid content of the polymer solution with the viscosity and solid content of the composition (B-1) in the above formula (i).
- the composition (B-1) can be prepared using a known method. For example, it can be prepared by synthesizing the copolymer (A-1) by the above-mentioned production method and blending the obtained copolymer (A-1) with an organic solvent or other components as necessary.
- the composition (B-1) can be used as it is or mixed with an antifouling agent or the like as necessary to obtain an antifouling coating composition.
- the composition (B-1) can be used for an anti-fogging coating composition, an anti-fogging coating composition, and the like.
- composition (B-2) contains the polymer solution of the second embodiment. Therefore, it contains a copolymer (A-2) and an organic solvent.
- the composition (B-2) may consist only of the polymer solution of the second aspect, or may further contain other materials in addition to the polymer solution of the second aspect. . Examples of other materials include diluting organic solvents and other components. Examples of the organic solvent for dilution include the same as those mentioned as the organic solvent for the polymer solution.
- the organic solvent in the polymer solution and the organic solvent for dilution may be the same or different. Other components are the same as described above.
- composition (B-2) preferred values for the content of the copolymer (A-2), the content of other components, the viscosity at 25 ° C., and the ratio (VX) determined by the formula (i) are as follows: Similar to the polymer solution.
- the content of the organic solvent in the composition (B-2) is 30% by mass or more with respect to the total amount (100% by mass) excluding the copolymer (A-2) of the composition (B-2). 45 mass% or more is preferable, and 50 mass% or more is more preferable. If content of an organic solvent is more than the said lower limit, the drying property of the coating film obtained will be excellent.
- the upper limit of the content of the organic solvent is not particularly limited, but can be, for example, 100% by mass or less based on the copolymer (A-2). When the content of the organic solvent is not more than the upper limit of the above range, an antifouling coating composition having a low VOC content can be obtained.
- the content of the organic solvent is the total amount of all the organic solvents contained in the composition (B-2).
- the water content of the composition (B-2) is preferably 15% by mass or less, and more preferably 10% by mass or less.
- the lower limit is not particularly limited, and may be 0% by mass.
- the water content is a ratio of water to the total mass of the composition (B-2). When the water content is not more than the above upper limit, the water resistance and drying property of the coating film formed from the antifouling coating composition containing the composition (B-2) are more excellent.
- the composition (B-2) can be prepared using a known method.
- it can be prepared by producing the polymer solution of the second embodiment by the above-described production method and, if necessary, blending the obtained polymer solution with an organic solvent for dilution or other components.
- the composition (B-2) can be used as it is or mixed with an antifouling agent or the like as necessary to obtain an antifouling coating composition.
- the composition (B-2) can be used for antifouling paint compositions, antifogging paint compositions and the like.
- composition (B-3) Another embodiment of the polymer-containing composition includes the polymer solution of the second embodiment, and the content of the organic solvent is 30% by mass or more based on the copolymer (A-2). And a composition (hereinafter also referred to as “composition (B-3)”).
- the content of the organic solvent in the composition (B-3) is preferably 45% by mass or more, and more preferably 50% by mass or more with respect to the copolymer (A-2).
- the upper limit of the content of the organic solvent is not particularly limited, and may be the same as, for example, the composition (B-2).
- the composition (B-3) may consist only of the polymer solution of the second aspect, or may further contain other materials in addition to the polymer solution of the second aspect. .
- the water content of the composition (B-3) is preferably 15% by mass or less, and more preferably 10% by mass or less.
- the lower limit is not particularly limited, and may be 0% by mass.
- the composition (B-3) can be prepared in the same manner as the composition (B-2).
- the composition (B-3) can be used as it is or mixed with an antifouling agent or the like as necessary to obtain an antifouling coating composition.
- the composition (B-3) can be used for antifouling paint compositions, antifogging paint compositions, and the like.
- the fifth aspect of the present invention is an antifouling paint composition comprising the composition (B-1) or the composition (B-2).
- the antifouling coating composition contains at least the copolymer (A-1).
- the antifouling coating composition contains the composition (B-2)
- the antifouling coating composition contains at least a copolymer (A-2) and an organic solvent.
- the antifouling coating composition preferably contains an organic solvent.
- the organic solvent in the antifouling coating composition may be an organic solvent derived from the composition (B-1), or an organic solvent not derived from the composition (B-1) (antifouling coating composition) Or a mixture thereof may be used.
- Examples of the organic solvent not derived from the composition (B-1) include the same organic solvents as those described above.
- the organic solvent in the antifouling coating composition may be only an organic solvent derived from the composition (B-2). It may be a mixture of an organic solvent derived from B-1) and an organic solvent not derived (mixed at the time of producing the antifouling coating composition).
- the antifouling coating composition of this aspect further contains an antifouling agent.
- the antifouling coating composition of the present invention may further contain other components other than the copolymer (A-1), the copolymer (A-2), the organic solvent and the antifouling agent.
- the other component may be derived from the composition (B), may not be derived (mixed during the production of the antifouling paint composition), or may be a mixture thereof. Good.
- Antifouling agent examples include an inorganic antifouling agent and an organic antifouling agent, and one or two or more can be appropriately selected and used according to the required performance.
- Antifouling agents include, for example, copper-based antifouling agents such as cuprous oxide, thiocyanic copper and copper powder, compounds of other metals (lead, zinc, nickel, etc.), amine derivatives such as diphenylamine, nitrile compounds, benzothiazole Compounds, maleimide compounds, pyridine compounds, and the like. These can be used individually by 1 type or in combination of 2 or more types.
- an antifouling agent 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, Manganese ethylene bisdithiocarbamate, zinc dimethyldithio Carbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate Rhodan copper, 4,5-dichloro-2-noctyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N′-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide , 2-pyridinethiol-1-oxide zinc salt, Tet Methyl thiura
- the antifouling agent is cuprous oxide, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3carbonitrile (hereinafter referred to as “antifouling agent (1)”. And at least one selected from the group consisting of triphenylborane and medetomidine.
- the content of the antifouling agent in the antifouling coating composition is not particularly limited, but is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the copolymer (A-1) or (A-2). More preferred is 150 parts by mass.
- the content of the antifouling agent is not less than the lower limit of the above range, the antifouling effect of the formed coating film is more excellent. If the content of the antifouling agent is not more than the upper limit of the above range, the self-polishing property is excellent.
- Examples of other components include polymers other than the copolymer (A-1) and the copolymer (A-2).
- the other polymer include thermoplastic resins (thermoplastic polymers) other than the copolymer (A-1) and the copolymer (A-2).
- the antifouling coating composition of this embodiment preferably contains a thermoplastic resin other than the copolymer (A-1) and the copolymer (A-2). When the antifouling coating composition contains the thermoplastic resin, the coating film properties such as crack resistance and water resistance are improved.
- thermoplastic resin other than the copolymer (A-1) and the copolymer (A-2) examples include chlorinated paraffin; chlorinated polyolefin such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ether; Polypropylene sebacate; partially hydrogenated terphenyl; polyvinyl acetate; (meth) methyl acrylate copolymer, (meth) ethyl acrylate copolymer, (meth) propyl acrylate copolymer, (meth) Poly (meth) acrylic acid alkyl ester such as butyl acrylate copolymer and (meth) acrylic acid cyclohexyl copolymer; polyether polyol; alkyd resin; polyester resin; vinyl chloride-vinyl acetate copolymer, vinyl chloride -Vinyl propionate copolymer, vinyl chloride-isobutyl vinyl ether copolymer, vinyl chloride
- thermoplastic resins may be used alone or in combination of two or more. Chlorinated paraffin is preferable in that it functions as a plasticizer and can improve the crack resistance and peel resistance of the coating film. Organic waxes such as semi-synthetic wax and synthetic wax are preferred in that they function as an anti-settling agent and an anti-sagging agent, and an effect of improving the storage stability and pigment dispersibility of the antifouling coating composition is obtained. Oxidized polyethylene wax and polyamide wax are more preferred.
- the content of the thermoplastic resin other than the copolymer (A-1) and the copolymer (A-2) in the antifouling coating composition is not particularly limited, but the copolymer (A-1) or (A -2) 0.1 to 50 parts by mass is preferable with respect to 100 parts by mass, and 0.1 to 10 parts by mass is more preferable. If the content of the thermoplastic resin is not less than the lower limit of the above range, the coating film properties such as crack resistance and water resistance are more excellent, and if it is not more than the upper limit of the above range, the hydrolyzability is more excellent.
- the antifouling paint composition may contain a silicon compound such as dimethylpolysiloxane and silicone oil, a fluorine-containing compound such as fluorinated hydrocarbon, etc. for the purpose of imparting lubricity to the coating film surface and preventing biological adhesion. Good.
- Antifouling paint compositions include various pigments, dehydrating agents, antifoaming agents, leveling agents, pigment dispersants (eg anti-settling agents), anti-sagging agents, matting agents, UV absorbers, antioxidants, and improved heat resistance. Agents, slip agents, preservatives, plasticizers, viscosity control agents and the like may be included.
- the pigment include zinc oxide, talc, silica, barium sulfate, potassium feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, dial, titanium oxide, phthalocyanine blue, kaolin, gypsum and the like. In particular, zinc oxide and talc are preferable.
- Examples of the dehydrating agent include silicate-based, isocyanate-based, orthoester-based, and inorganic-based materials. More specifically, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ortho boron ester, tetraethyl orthosilicate, anhydrous gypsum, calcined gypsum, synthetic zeolite (molecular sieve) and the like can be mentioned. In particular, a molecular sieve is preferable.
- moisture can be supplemented and storage stability can be improved.
- anti-settling agents and anti-sagging agents other than thermoplastic resins include bentonite-based, finely divided silica-based, stearate salt, lecithin salt, alkyl sulfonate, and the like.
- plasticizers other than thermoplastic resins include phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate; aliphatic dibasic ester plasticizers such as isobutyl adipate and dibutyl sebacate ; Glycol ester plasticizers such as diethylene glycol dibenzoate and pentaerythritol alkyl ester; phosphate ester plasticizers such as tricresyl phosphate (TCP), triaryl phosphate and trichloroethyl phosphate; epoxy soybean oil, octyl epoxy stearate, etc.
- phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate
- aliphatic dibasic ester plasticizers such as isobutyl
- organic tin plasticizers such as dioctyltin laurate and dibutyltin laurate
- trioctyl trimellitic acid triacetylene and the like.
- the antifouling coating composition may or may not contain water.
- the moisture content of the antifouling coating composition is preferably 15% by mass or less, and more preferably 10% by mass or less.
- the lower limit is not particularly limited, and may be 0% by mass.
- the water content is a ratio of water to the total mass of the antifouling coating composition. When the water content is not more than the above upper limit value, the water resistance and drying property of the coating film formed from the antifouling coating composition are more excellent.
- the VOC content of the antifouling coating composition of the present invention is preferably 500 g / L or less, more preferably 420 g / L or less, further preferably 400 g / L or less, and particularly preferably 380 g / L or less.
- the VOC content is calculated from the following formula using the specific gravity and the solid content of the antifouling coating composition.
- VOC content (g / L) specific gravity of composition ⁇ 1000 ⁇ (100 ⁇ solid content) / 100
- the specific gravity and solid content of the antifouling coating composition are each measured by the method described in the examples described later.
- the VOC content can be adjusted by the content of the organic solvent.
- the heating residue of the antifouling coating composition is preferably 70 to 100% by mass, more preferably 70 to 90% by mass, and further preferably 75 to 80% by mass. If the heating residue of the antifouling coating composition is at least the lower limit of the above range, the VOC content will be sufficiently low. If the heating residue is not more than the upper limit of the above range, the viscosity of the antifouling coating composition can be easily lowered. The heating residue is measured by the measuring method shown in the examples described later.
- the viscosity at 25 ° C. of the antifouling coating composition of the present invention is preferably less than 5,000 mPa ⁇ s, more preferably less than 4,000 mPa ⁇ s, still more preferably less than 3,000 mPa ⁇ s, and 2,000 mPa ⁇ s. -Less than s is particularly preferable. If the antifouling paint composition has a viscosity equal to or lower than the upper limit, coating is easy. The lower limit of the viscosity at 25 ° C.
- the antifouling coating composition is not particularly limited, but is preferably 100 mPa ⁇ s or more, more preferably 200 mPa ⁇ s or more, and even more preferably 300 mPa ⁇ s or more in terms of suppression of coating sagging during coating. 1,000 mPa ⁇ s or more is particularly preferable. Therefore, the viscosity at 25 ° C.
- the antifouling coating composition is preferably 100 mPa ⁇ s or more and less than 5,000 mPa ⁇ s, more preferably 200 mPa ⁇ s or more and less than 4,000 mPa ⁇ s, and more preferably 300 mPa ⁇ s or more and 3, It is more preferably less than 000 mPa ⁇ s, particularly preferably not less than 500 mPa ⁇ s and less than 2,000 mPa ⁇ s.
- the viscosity of the antifouling coating composition can be adjusted by the viscosity of the composition (B), the amount of organic solvent added to the composition (B), and the like.
- the antifouling paint composition can be prepared by preparing the composition (B), adding an antifouling agent, other components and an organic solvent as necessary, and mixing them.
- the antifouling paint composition of this aspect is for forming a paint film (antifouling paint film) on the surface of a base material such as an underwater structure such as a ship, various fishing nets, a port facility, an oil fence, a bridge, and a submarine base.
- a coating film using the antifouling coating composition of this embodiment can be formed on the substrate surface directly or via a base coating film.
- the undercoat film can be formed using a wash primer, a chlorinated rubber-based or epoxy-based primer, an intermediate coating, or the like.
- the coating film can be formed by a known method.
- an antifouling coating composition is applied to the surface of a substrate or a base coating on the substrate by means of brush coating, spray coating, roller coating, immersion coating, or the like, and dried to dry the coating film.
- the coating amount of the antifouling coating composition can generally be set to an amount that results in a dry coating film thickness of 10 to 400 ⁇ m.
- the coating film can be usually dried at room temperature, and may be heat-dried as necessary.
- the monomer mixture may further include a monomer (c).
- the composition of the monomer mixture is the same as that of the copolymer (A-2) set according to the composition of the (meth) acrylic copolymer to be produced. That is, the type of monomer constituting the monomer mixture and the content (% by mass) of each monomer with respect to the total mass of all the monomers are the respective constituents of the (meth) acrylic copolymer to be produced. It is the same as the content (mass%) of each structural unit with respect to the kind of the structural unit derived from a monomer, and the total mass of all the structural units.
- the (meth) acrylic copolymer produced by the production method of this embodiment is preferably the copolymer (A-1) or the copolymer (A-2).
- a known polymerization method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be applied.
- the solution polymerization method is preferable in terms of productivity and coating film performance.
- the polymerization may be performed by a known method using a known polymerization initiator. For example, a method of reacting the monomer mixture described above in the presence of a radical polymerization initiator at a reaction temperature of 60 to 180 ° C. (more preferably 60 to 120 ° C.) for 4 to 14 hours (more preferably 5 to 10 hours). It is done.
- a chain transfer agent may be used as necessary.
- radical polymerization initiator known ones can be used. For example, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2- Azo compounds such as methylbutyronitrile; organic compounds such as lauryl peroxide, benzoyl peroxide, cumene hydroperoxide, lauryl peroxide, di-t-butyl peroxide, t-butylperoxy-2-ethylhexanoate Peroxides; and the like.
- the content of the polymerization initiator is not particularly limited and can be set as appropriate. Typically, it is about 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
- chain transfer agent known ones can be used, and examples thereof include mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, ⁇ -methylstyrene dimer, terpinolene and the like.
- the content of the chain transfer agent is not particularly limited and can be set as appropriate. Typically, the amount is about 0.0001 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
- the solvent used in the solution polymerization is not particularly limited, and a general organic solvent can be used.
- a general organic solvent can be used.
- it can be appropriately selected from the organic solvents mentioned above.
- the method for producing the (meth) acrylic copolymer of this embodiment a monomer mixture containing the monomer (a) and the macromonomer (b) is polymerized, and thus the (meth) acrylic product obtained is obtained.
- the copolymer can achieve the same effects as the copolymer (A-1) of the first aspect and the polymer solution of the second aspect.
- the hardness and water resistance of a coating film using this (meth) acrylic copolymer are excellent.
- This coating film is also excellent in static antifouling properties in seawater or the like, and exhibits an excellent antifouling effect stably over a long period of time.
- the reason why the coating film using the (meth) acrylic copolymer obtained by the production method of this embodiment is excellent in hardness is that it contains a structural unit derived from the macromonomer (b).
- the reason why the coating film is excellent in water resistance may be that the hardness of the coating film is high.
- a monomer mixture containing a macromonomer and a carboxy group-containing ethylenically unsaturated monomer and not containing a divalent metal-containing ethylenically unsaturated monomer is polymerized, and then divalent.
- a monomer composition containing a metal-containing ethylenically unsaturated monomer is dropped and polymerized to obtain a vinyl polymer, and then a water-based antifouling paint resin composition in which the vinyl polymer is dispersed in water by adding water.
- a coating film using the resin composition for an aqueous antifouling paint obtained by this method is inferior in water resistance. This is due to the fact that the macromonomer and the divalent metal-containing ethylenically unsaturated monomer are mixed in different monomer mixtures, and that the amine is included to make an aqueous dispersion. It is thought that there is.
- the hardness of the coating film after 1 day is also inferior. This is thought to be due to the low drying property due to the aqueous system.
- the preliminary drying is a process for extending the measurement sample over the entire dish and facilitating volatilization of the organic solvent by the main drying.
- the measurement sample and toluene were dissolved by heating in a water bath at 70 to 80 ° C. and evaporated to dryness. After preliminary drying, main drying was performed for 2 hours with a hot air dryer at 105 ° C.
- a measurement sample was put in a dried Gardner bubble viscosity tube (hereinafter also simply referred to as a viscosity tube) up to the indication line of the viscosity tube, and the tube was stoppered with a cork stopper.
- the viscosity tube from which the measurement sample was collected was immersed vertically in a constant temperature water bath adjusted to a specified temperature (25.0 ⁇ 0.1 ° C.) for at least 2 hours to make the measurement sample constant temperature,
- the viscosity tube (Gardner viscosity) was determined by simultaneously rotating the viscosity tube containing the measurement sample by 180 ° and comparing the hour rise rate of the measurement sample with that of the reference tube.
- B type viscosity The viscosity of the measurement sample was measured with a B-type viscometer at 25 ° C., and the value was shown as the B-type viscosity.
- a meta (acrylic) copolymer containing the structural unit (A-3) It measured using the gel permeation chromatography (GPC) (HLC-8220 by Tosoh Corporation).
- GPC gel permeation chromatography
- An N, N-dimethylformamide (DMF) solution was prepared so that the meta (acrylic) copolymer was 0.4% by mass, and a Tosoh column (TSKgel ⁇ -M (Tosoh Corporation, 7.8 mm ⁇ 30 ⁇ m), TSK guard column ⁇ (Tosoh Corporation, 6.0 mm ⁇ 4 cm)) was put into a device, and 100 ⁇ l of the above solution was injected, and measurement was performed at 40 ° C.
- TSKgel ⁇ -M Tosoh Corporation, 7.8 mm ⁇ 30 ⁇ m
- TSK guard column ⁇ Tosoh Corporation, 6.0 mm ⁇ 4 cm
- the weight average molecular weight (Mw) or number average molecular weight (Mn) was calculated in terms of standard polystyrene.
- VOC content The VOC content of the measurement sample was calculated by the following formula.
- VOC content (g / L) specific gravity of measurement sample ⁇ 1000 ⁇ (100 ⁇ solid content) / 100
- the specific gravity of the measurement sample was calculated by filling the measurement sample in a specific gravity cup having a capacity of 100 mL at 25 ° C. and measuring the mass.
- the polymer-containing composition was applied with a 500 ⁇ m applicator and dried at 25 ° C. for 1 week to form a coating film to obtain a test plate.
- Martens hardness (HM) was measured with the ultra micro hardness meter (Fischer Instruments Co., Ltd. product, brand name: HM2000).
- Martens hardness was measured at three different points on the same coating film, and the average value thereof was defined as the hardness of the coating film.
- the Martens hardness (HM) is in the range of 1.2 ⁇ 15.0N / mm 2, and more preferably in the range of 2.0 ⁇ 10.0N / mm 2.
- the coating film hardness was measured in the same manner, except that the drying time was 1 day at 25 ° C.
- the antifouling paint composition was applied to a hard vinyl chloride plate of 50 mm ⁇ 50 mm ⁇ 2 mm (thickness) with an applicator so as to have a dry film thickness of 120 ⁇ m, dried to form a coating film, and a test plate was obtained. .
- the test plate was attached to a rotating drum installed in seawater, rotated at a peripheral speed of 7.7 m / s (15 knots), and the film thickness of the coating film after 3 months was measured.
- the consumed film thickness per month ((120 ⁇ m ⁇ measured film thickness ( ⁇ m)) / 3) was calculated from the measured film thickness, and the value was used as the degree of wear.
- the degree of wear is preferably 1 to 30 ⁇ / M.
- the antifouling paint composition is applied to a sandblasted steel sheet having a 150 mm ⁇ 70 mm ⁇ 1.6 mm (thickness) pre-coated antirust paint with a brush so that the dry film thickness is 120 ⁇ m and dried.
- a coating film was formed to obtain a test plate. After immersing this test plate in the sea and allowing it to stand for 3 months, the ratio of the area where marine organisms attached to the total area of the coating (area where marine organisms adhered) (%) was determined. When it was 30% or less, the anti-staining property was considered good.
- Monomer (a1-1) 1-butoxyethyl methacrylate (synthetic product synthesized in Production Example a1-1 described later).
- Monomer (a1-2) 1-isobutoxyethyl methacrylate (synthetic product synthesized in Production Example a1-2 described later).
- Monomer (a1-3) 1- (2-ethylhexyloxy) ethyl methacrylate (synthetic product synthesized in Production Example a1-3 described later).
- Monomer (a2-1) Triisopropylsilyl acrylate (TIPX).
- Monomer (a3-1) Metal-containing monomer mixture (synthetic product synthesized in Production Example a3-1 described later).
- Monomer (a3-2) Metal-containing monomer mixture (synthetic product synthesized in Production Example a3-2 described later).
- Macromonomer (MM1) A macromonomer having a number average molecular weight of 1600 obtained in Production Example MM1 described later.
- Macromonomer (MM2) A macromonomer having a number average molecular weight of 2500 obtained in Production Example MM2 described later.
- Macromonomer (MM3) A macromonomer having a number average molecular weight of 3600 obtained in Production Example MM3 described later.
- Macromonomer (MM4) A macromonomer having a number average molecular weight of 6700 obtained in Production Example MM4 described later.
- MMA methyl methacrylate.
- MA methyl acrylate.
- EA ethyl acrylate.
- BA n-butyl acrylate.
- MTMA 2-methoxyethyl methacrylate.
- MTA 2-methoxyethyl acrylate.
- MAA methacrylic acid.
- AIBN 2,2′-azobisisobutyronitrile.
- AMBN 2,2′-azobis (2-methylbutyronitrile).
- NOFMER MSD trade name, manufactured by NOF Corporation, ⁇ -methylstyrene dimer.
- Antifouling agent (1) 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile.
- Additive (1) Toyoparax (registered trademark) 150 (manufactured by Tosoh Corporation, chlorinated paraffin).
- Additive (2) Disparon (registered trademark) 4200-20 (manufactured by Enomoto Kasei Co., Ltd., oxidized polyethylene wax).
- Additive (3) Disparon A603-20X (manufactured by Enomoto Kasei Co., Ltd., polyamide wax).
- MMA was continuously added dropwise at a rate of 0.24 part / minute for 75 minutes using a dropping pump.
- the reaction solution was held at 60 ° C. for 6 hours and then cooled to room temperature to obtain Dispersant 1 having a solid content of 10% by mass as a transparent aqueous solution.
- MM1 The number average molecular weight of the macromonomer (MM1) was 1600.
- ⁇ Production example MM2> In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant 1 (solid content 10% by mass) were stirred and stirred uniformly. Solution. Next, 100 parts of MMA, 0.004 part of chain transfer agent 1 and 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (Perocta O (registered trademark), manufactured by NOF Corporation ) 0.4 parts was added to make an aqueous suspension. Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 80 ° C.
- MM2 The number average molecular weight of the macromonomer (MM2) was 2500.
- ⁇ Production example MM3> In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant 1 (solid content 10% by mass) were stirred and stirred uniformly. Solution. Next, 100 parts of MMA, 0.003 part of chain transfer agent 1, and 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (Perocta O, manufactured by NOF Corporation) 0.3 Part was added to form an aqueous suspension. Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 80 ° C.
- MM3 The number average molecular weight of the macromonomer (MM3) was 3600.
- ⁇ Production example MM4> In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant 1 (solid content 10% by mass) were stirred and stirred uniformly. Solution. Next, 100 parts of MMA, 0.0015 part of chain transfer agent 1, and 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (Perocta O, manufactured by NOF Corporation) 0.15 Part was added to form an aqueous suspension. Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 80 ° C.
- MM4 The number average molecular weight of the macromonomer (MM4) was 6700.
- ⁇ Production example MM5> In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant 1 (solid content 10% by mass) were stirred and stirred uniformly. Solution. Next, 75 parts of MMA, 25 parts of MTMA, 0.01 part of chain transfer agent 1 and 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (Perocta O, manufactured by NOF Corporation) 1.5 parts was added to make an aqueous suspension. Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 80 ° C.
- MM5 The number average molecular weight of the macromonomer (MM5) was 2000.
- Example 1 A reaction vessel equipped with a stirrer, a temperature controller, and a dropping funnel was charged with 48.3 parts of xylene and heated to 85 ° C. with stirring in a nitrogen atmosphere. Subsequently, a mixture of 25 parts of monomer (a1-1), 10 parts of macromonomer (MM1), 7.5 parts of MMA, 20 parts of EA, 37.5 parts of MTMA, and 1.5 parts of AIBN was added from the dropping funnel over 4 hours. It was dropped at a constant speed.
- Table 1 shows the characteristic values (solid content (mass%), Gardner viscosity, B-type viscosity of the obtained polymer-containing compositions A-1 to A-11, and the copolymer contained in each polymer-containing composition. Number average molecular weight (Mn) and weight average molecular weight (Mw)) are described. The solid content of the polymer-containing compositions A-1 to A-11 is equal to the content of the copolymer. Table 1 shows the performance (water resistance 1, coating film hardness) of the coating film formed using the polymer-containing composition.
- the polymer-containing compositions A-1 to A-5 and A-7 to A-10 of Examples 1 to 9 had high viscosity but low viscosity. Moreover, the hardness and water resistance of the formed coating film were favorable.
- Examples 10 to 20, Comparative Examples 3 to 4> In accordance with the composition shown in Table 2, after each component was charged into a metal can, 70 g of glass beads were added, and the mixture previously mixed with a stirring rod was dispersed with a rocking shaker to obtain an antifouling paint composition. It was. The evaluation results of the obtained antifouling paint composition are shown in Table 2.
- the numerical value described in the column of composition indicates the blending amount (part).
- the blending amount of the polymer-containing composition is the amount of the entire polymer-containing composition.
- the antifouling paint compositions of Examples 10 to 20 had high solid content and low VOC, but had low viscosity and good coating suitability. Further, the degree of wear of the formed coating film is good, and from the results of Examples 1 to 9, it can be judged that the hardness and water resistance of the coating film are also good.
- the antifouling coating composition of Comparative Example 3 using a copolymer containing no structural unit based on a macromonomer was compared with Examples 10 to 14 having the same composition except for the polymer-containing composition. Were at the same level, but the paint viscosity was high and the paintability was poor. A similar tendency was observed in the comparison between Comparative Example 4 and Examples 18 to 20. When the antifouling property of the antifouling coating composition of Example 10 and Comparative Example 3 was evaluated, the results were good.
- Example 21 A reaction vessel equipped with a stirrer, a temperature controller, and a dropping funnel was charged with 40 parts of xylene and 10 parts of macromonomer (MM2), and the temperature was raised to 90 ° C. while stirring. Subsequently, under a nitrogen atmosphere, a mixture of 50 parts of TIPX, 25 parts of MMA, 10 parts of EA, 5 parts of MTA, and 1.0 part of AMBN was dropped from the dropping funnel over a period of 4 hours.
- MM2 macromonomer
- Example 5 Solution-like polymer-containing compositions A-13 to A-14, A in the same manner as in Example 21 except that the amount (parts) of monomer and initiator AIBN were as shown in Table 1. -16 was produced.
- Example 24 A reaction vessel equipped with a stirrer, a temperature controller, and a dropping funnel was charged with 40 parts of xylene and heated to 90 ° C. while stirring. Subsequently, under a nitrogen atmosphere, a mixture consisting of 50 parts of TIPX, 10 parts of macromonomer (MM2), 25 parts of MMA, 10 parts of EA, 5 parts of MTA and 1.0 part of AMBN was dropped from the dropping funnel at a constant rate over 4 hours. 30 minutes after the completion of dropping, 1.0 part of t-butylperoxy 2-ethylhexanoate and 26 parts of xylene were added dropwise over 1 hour and a half, and the mixture was further stirred for 1 hour. A solution-like polymer-containing composition (polymer solution) A-15 having a viscosity of 690 mPa ⁇ s was obtained.
- Table 3 shows the characteristic values of the obtained polymer-containing compositions A-12 to A-16 (solid content (mass%), amount of organic solvent (mass%), B-type viscosity, included in each polymer-containing composition.
- the number average molecular weight (Mn), weight average molecular weight (Mw) and acid value) of the copolymer to be prepared are described.
- the solid content of the polymer-containing compositions A-12 to A-16 is equal to the content of the copolymer.
- Table 3 shows the performance (coating film hardness, coating film hardness after 1 day, water resistance 2) of the coating film formed using the polymer-containing composition.
- the polymer-containing compositions A-12 to A-15 of Examples 21 to 24 had high viscosity but low viscosity. Moreover, the hardness and water resistance of the formed coating film were favorable.
- the polymer-containing composition A-16 of Comparative Example 5 that did not use the macromonomer had the same solid content but higher viscosity than Examples 21 to 24. Moreover, the coating film hardness and the coating film hardness 1 day after coating were low. Although the water resistance of the coating film was good, it was inferior to Examples 21 to 24.
- the numerical value described in the column of composition indicates the blending amount (part).
- the blending amount of the polymer-containing composition is the total amount of the polymer-containing composition.
- the antifouling paint compositions of Examples 25 to 28 had a sufficient degree of wear. Further, from the results of Examples 21 to 24, it can be judged that the coating film hardness, the coating film hardness after one day and the water resistance are also excellent.
- the coating film of the antifouling coating composition of Comparative Example 6 had a sufficient degree of wear. From the results of Comparative Example 5, the coating film hardness, the coating film hardness after 1 day, and the water resistance of Examples 25 to It can be judged that it is inferior to 28. When the antifouling paint compositions of Examples 25 to 28 and Comparative Example 6 were evaluated for static resistance, the results were good.
- Example 29 A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 30 parts of xylene and 4.0 parts of EA and heated to 100 ° C. while stirring.
- PGM propylene glycol methyl ether
- Examples 30 to 34, 42 to 46, Comparative Example 7> A solution-like polymer-containing composition (polymer solution) A-18 to A-22, A— was prepared in the same manner as in Example 29 except that the amounts of the monomers were as shown in Tables 5 to 6. 30 to A-33 and A-35 to 36 were produced. The blending amount of the monomer (a3) in Tables 5 to 6 describes only the solid content.
- Example 35 A pressure-polymerizable autoclave equipped with a cooler, thermometer, dripping tank and stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 30 parts of xylene and 4 parts of EA, pressurized to 350 kPa while stirring and heated to 145 ° C. Warm up. Subsequently, 35 parts of MMA, 5 parts of EA, 30 parts of BA, 28.8 parts of monomer (a3-1) obtained in Production Example a3-1 (total amount including organic solvent), chain transfer agent (Nippon Yushi) A transparent mixture composed of 1.5 parts of Nofmer MSD (trade name) and 6 parts of AMBN was added dropwise at a constant rate over 4 hours.
- Examples 36 to 41, 47> A solution-like polymer-containing composition (polymer solution) A-24 to A-29, A- was prepared in the same manner as in Example 35, except that the amounts of monomers charged were as shown in Tables 5 to 6. 37 was produced. The blending amount of the monomer (a3) in Tables 5 to 6 describes only the solid content.
- ⁇ Comparative Example 8> A reaction vessel equipped with a stirrer, a temperature controller, and a dropping device was charged with 15 parts of xylene and heated to 130 ° C. while stirring. Thereafter, a mixture of the following raw materials was dropped at a constant rate over 2 hours, and a copolymerization reaction was further performed for 0.5 hours.
- Tables 5 to 6 show the types and amounts of materials used for the production of the polymer-containing composition, the characteristic values of the obtained polymer-containing compositions A-17 to A-37 (solid content (mass%), organic solvent The amount (mass%), B-type viscosity, weight average molecular weight (Mw), number average molecular weight (Mn), acid value) of the copolymer contained in each polymer-containing composition are described. The solid content of the polymer-containing compositions A-17 to A-37 is equal to the content of the copolymer.
- Tables 5 to 6 show the performance of the coating film formed using the polymer-containing composition (coating film hardness, coating film hardness after 1 day, water resistance 2).
- the coating films of the polymer-containing compositions of Examples 29 to 47 were excellent in hardness and water resistance. Moreover, the coating film hardness after one day was high. The coating film of the resin composition of Comparative Example 7 in which no macromonomer was used was inferior in both hardness and water resistance. Moreover, the viscosity of the polymer-containing composition was high. It is an aqueous dispersion in which a polymer solution having a B-type viscosity at 25 ° C.
- the coating film of the polymer-containing composition of Comparative Example 8 had a low coating film hardness after 1 day and was inferior in water resistance. Further, the polymer solution had a high viscosity and the handling property was low.
- Examples 48 to 68, Comparative Examples 9 to 10> According to the compositions shown in Tables 7 to 8, each component was mixed with a high-speed disper to obtain an antifouling paint composition. Tables 7 to 8 show the evaluation results of the performance (degree of wear) of the coating film formed using the obtained antifouling coating composition.
- the numerical values described in the column of composition indicate the blending amount (parts).
- the blending amount of the polymer-containing composition is the total amount of the polymer-containing composition.
- the coating films of the antifouling coating compositions of Examples 48 to 68 had a sufficient degree of wear. Further, from the results of Examples 29 to 47, it can be judged that the coating film hardness, the coating film hardness after one day and the water resistance are also excellent. Although the coating film of the antifouling coating composition of Comparative Example 9 had a sufficient degree of wear, it can be judged from the results of Comparative Example 7 that the coating film hardness, coating film hardness after 1 day, and water resistance are low. . The coating film of the antifouling paint composition of Comparative Example 10 was less consumed than Examples 48-68. Therefore, it can be determined that the antifouling property is poor. From the result of Comparative Example 8, it can be determined that the water resistance is low. When the antifouling property of the antifouling coating compositions of Examples 48 and 51 and Comparative Example 9 was evaluated, the results were good.
- the (meth) acrylic copolymer, polymer solution and polymer-containing composition of the present invention can be used for antifouling paint compositions, antifogging paint compositions, etc., and particularly suitable for antifouling paint compositions. Can be used.
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Abstract
Description
本願は、2015年9月25日に、日本に出願された特願2015-188349号、及び2015年9月29日に、日本に出願された特願2015-190946号に基づき優先権を主張し、その内容をここに援用する。
防汚塗料として、自己研磨型の防汚塗料が知られている。自己研磨型の防汚塗料は、典型的には、加水分解性樹脂と防汚剤とを含む。この防汚塗料から得られる塗膜は、塗膜表面が徐々に海水に溶解して表面更新(自己研磨)され、塗膜表面に常に防汚成分が露出することにより、長期にわたって防汚効果を発揮する。
(1)無機金属化合物とカルボキシ基含有ラジカル重合性単量体の反応物と、少なくともアルコール系溶剤を含む有機溶剤と、特定量の水とからなる金属含有モノマー混合物と、その他のラジカル重合性不飽和単量体とを共重合した樹脂組成物(特許文献1)。
(2)カルボキシ基含有エチレン性不飽和単量体と、2価金属含有エチレン性不飽和単量体と、ラジカル重合性基を有するマクロモノマーとを特定の手順で重合させたビニル系ポリマーを、水を含む分散媒に分散させた樹脂組成物(特許文献2)。
有機溶剤の含有量が抑えられた防汚塗料用組成物として、前記特許文献2の樹脂組成物が提案されている。
さらに、この樹脂組成物は、有機溶剤の含有量を少なくして高固形分化しようとすると、高粘度になり防汚塗料の調製や塗装が困難となるため、高固形分化が難しい問題もある。
さらに、この防汚塗料用組成物には有機溶剤が多量に含まれており、この防汚塗料用組成物を用いた防汚塗料はVOC含有量が多い。有機溶剤の含有量を減らせばVOCは低減されるが、固形分が増えることで粘度が上昇し、防汚塗料の調製や塗装が困難となる。
〔1〕下記式(1)、下記式(2)又は下記式(3)で表される構造からなる群から選ばれる少なくとも1種の構造(I)を有する構成単位(A1)、及びトリオルガノシリルオキシカルボニル基を有する構成単位(A2)からなる群から選ばれる少なくとも1種の構成単位と、マクロモノマー(b)由来の構成単位(B)と、を有する(メタ)アクリル系共重合体。
〔2〕下記式(4)又は(5)で表される構造からなる群から選ばれる少なくとも1種の構造(III)を有する構成単位(A3)と、マクロモノマー(b)由来の構成単位(B)と、を有する(メタ)アクリル系共重合体と、
有機溶剤と、を含み、
25℃における粘度が、5×104mPa・s以下である、重合体溶液。
-COO-M-OCO ・・・(4)
-COO-M-R32 ・・・(5)
(式中、MはZn、Cu、Mg又はCaを示し、R32は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。)
〔3〕〔2〕に記載の重合体溶液を含み、有機溶剤の含有量が、前記(メタ)アクリル系共重合体を除いた全量に対して30質量%以上である、重合体含有組成物。
〔4〕水分含有量が15質量%以下である、〔3〕に記載の重合体含有組成物。
〔5〕前記マクロモノマー(b)が、下記式(b’)で表される構成単位を2以上有する、数平均分子量が500~50000であるマクロモノマーである、〔1〕に記載の(メタ)アクリル系共重合体。
〔6〕前記マクロモノマー(b)が、下記式(b’)で表される構成単位を2以上有する、数平均分子量が500~50000であるマクロモノマーである、〔2〕に記載の重合体溶液。
〔7〕前記マクロモノマー(b)が、下記式(b’)で表される構成単位を2以上有する、数平均分子量が500~50000であるマクロモノマーである、〔3〕又は〔4〕に記載の重合体含有組成物。
〔8〕〔1〕に記載の(メタ)アクリル系共重合体を含む、重合体含有組成物。
〔9〕前記(メタ)アクリル系共重合体が前記構成単位(A1)を有し、
下記式(11)で表される化合物、下記式(12)で表される化合物、及び下記式(13)で表される化合物からなる群から選ばれる少なくとも1種のアルケニル化合物をさらに含む、〔8〕に記載の重合体含有組成物。
〔10〕〔3〕、〔4〕、〔7〕~〔9〕のいずれかに記載の重合体含有組成物を含む、防汚塗料組成物。
〔11〕防汚剤をさらに含む、〔10〕に記載の防汚塗料組成物。
〔12〕前記防汚剤が、亜酸化銅、4-ブロモ-2-(4-クロロフェニル)-5-(トリフルオロメチル)-1H-ピロール-3-カルボニトリル、トリフェニルボラン及びメデトミジンからなる群から選ばれる少なくとも1種を含む、〔11〕に記載の防汚塗料組成物。
〔13〕25℃における粘度が、5000mPa・s以下である、〔10〕~〔12〕のいずれかに記載の防汚塗料組成物。
〔14〕VOC含有量が、500g/L以下である、〔10〕~〔13〕のいずれかに記載の防汚塗料組成物。
〔15〕前記(メタ)アクリル系共重合体以外の熱可塑性樹脂をさらに含む、〔10〕~〔14〕のいずれかに記載の防汚塗料組成物。
〔16〕下記式(1)、下記式(2)又は下記式(3)で表される構造からなる群から選ばれる少なくとも1種の構造(I)を有する単量体(a1)、トリオルガノシリルオキシカルボニル基を有する単量体(a2)、及び下記式(a3-1)で表される単量体及び下記式(a3-2)で表される単量体からなる群から選ばれる少なくとも1種の単量体(a3)からなる群から選ばれる少なくとも1種の単量体(a)と、
マクロモノマー(b)と、
を含む単量体混合物を重合して(メタ)アクリル系共重合体を得る工程を含む、(メタ)アクリル系共重合体の製造方法。
CH2=C(R31)-CO-O-M-R32 ・・・(a3-2)
(式中、Xは-O-、-S-又は-NR14-を示し、R14は水素原子又はアルキル基を示し、R1及びR2はそれぞれ、水素原子又は炭素数1~10のアルキル基を示し、R3及びR5はそれぞれ、炭素数1~20のアルキル基、シクロアルキル基又はアリール基を示し、R4及びR6はそれぞれ、炭素数1~10のアルキレン基を示し、MはZn、Cu、Mg又はCaを示し、R31は水素原子又はメチル基を示し、R32は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。)
「VOC」とは、常温常圧で容易に揮発する有機化合物(揮発性有機化合物)を意味する。
「構成単位」は、重合反応によって単量体から直接形成されたものであってもよく、重合反応によって得られた重合体を処理することによって、前記重合体が有する前記構成単位の構造の一部が別の構造に変換された構成単位であってもよい。
「単量体」は、重合性を有する化合物(重合性単量体)を意味する。
「(メタ)アクリレート」は、アクリレート及びメタクリレートの総称であり、「(メタ)アクリル酸」は、アクリル酸とメタクリル酸の総称であり、「(メタ)アクリロイル基」は、アクリロイル基とメタクリロイル基の総称であり、「(メタ)アクリロニトリル」は、アクリロニトリルとメタクリロニトリルの総称であり、「(メタ)アクリルアミド」は、アクリルアミドとメタクリルアミドの総称である。
「(メタ)アクリル系共重合体」は、構成単位の少なくとも一部が(メタ)アクリル系単量体由来の構成単位である共重合体を意味する。(メタ)アクリル系重合体は、(メタ)アクリル系単量体以外の単量体(例えばスチレン等のビニル系単量体)由来の構成単位をさらに有していてもよい。
「(メタ)アクリル系単量体」は、(メタ)アクリロイル基を有する単量体を意味する。
「粘度」は、特に規定のない場合は、B型粘度計により測定される値を意味する。
本発明の第一の態様は、構造(I)を有する構成単位(A1)及びトリオルガノシリルオキシカルボニル基を有する構成単位(A2)からなる群から選ばれる少なくとも1種の構成単位と、マクロモノマー(b)由来の構成単位(B)と、を有する(メタ)アクリル系共重合体(以下、「共重合体(A-1)」ともいう。)である。
共重合体(A-1)は、必要に応じて、構造(III)を有する構成単位(A3)をさらに有することができる。
共重合体(A-1)は、構成単位(A1)~(A3)及び構成単位(B)以外の他の構成単位(C)をさらに有することができる。
構成単位(A1)は、下記式(1)、下記式(2)又は下記式(3)で表される構造からなる群から選ばれる少なくとも1種の構造(I)を有する。
R1及びR2におけるアルキル基の炭素数は、1~4が好ましく、1~3がより好ましく、1又は2がさらに好ましい。
シクロアルキル基としては、炭素数4~8のシクロアルキル基が好ましく、例えばシクロヘキシル基、シクロペンチル基等が挙げられる。
アリール基としては、炭素数6~20のアリール基が好ましく、例えばフェニル基、ナフチル基等が挙げられる。
R3としては、炭素数1~10のアルキル基、シクロアルキル基が好ましい。
置換基としてのシクロアルキル基、アリール基はそれぞれ、前記と同様のものが挙げられる。アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられる。アルカノイルオキシ基としては、エタノイルオキシ基等が挙げられる。アラルキル基としては、ベンジル基等が挙げられる。
R4におけるアルキレン基の炭素数は、2~7が好ましく、3~4がより好ましい。
前記アルキレン基は、シクロアルキル基、アリール基、アルコキシル基、アルカノイルオキシ基、アラルキル基及びアセトキシ基からなる群から選ばれる置換基により置換されていてもよい。置換基により置換されている場合、置換基の数は1つでもよく2つ以上でもよい。アルキレン基に置換してもよい置換基の具体例としては、R3における置換基と同様のものが挙げられる。
R6は、式(2)中のR4と同様であり、好ましい態様も同様である。
単量体(a1)としては、構造(I)とエチレン性不飽和結合(重合性炭素-炭素二重結合)とを有する単量体が挙げられる。この場合、単量体(a1)単位は、単量体(a1)のエチレン性不飽和結合が開裂して単結合となった構造を有する。
単量体(a1)は、共重合体(A-1)を有機溶剤に溶解したときの粘度が低くなる点から、エチレン性不飽和結合を1つ有する単官能単量体であることが好ましい。
CH(CH3)=CH-COO-は、クロトノイルオキシ基(エチレン性不飽和結合がトランス型)又はイソクロトノイルオキシ基(エチレン性不飽和結合がシス型)である。
CHRX=CH-COO-は、カルボキシ基がヘミアセタールエステル基、ヘミケタールエステル基又はアルキルエステル基に置換された、マレイノイルオキシ基(エチレン性不飽和結合がシス型)又はフマロイルオキシ基(エチレン性不飽和結合がトランス型)である。
RXにおける構造(I)は、前記と同様である。RXが構造(I)である場合、RXは、Zが結合した基と同じ構造を有することが好ましい。例えば式(a1-1)で表される化合物の場合、RXは、-CR1R2-XR3で表される基であることが好ましい。
RXにおけるアルキルエステル基は、-COORX1で表される。RX1はアルキル基を示す。RX1のアルキル基としては、炭素数1~6のアルキル基が好ましく、メチル基が特に好ましい。
CH2=C(CH2RX)-COO-又はCH2=CRX-CH2COO-は、カルボキシ基がヘミアセタールエステル基、ヘミケタールエステル基又はアルキルエステル基に置換されたイタコノイルオキシ基である。RXは前記と同様である。
Zとしては、CH2=CH-COO-又はCH(CH3)=CH-COO-が好ましい。
例えば、カルボキシ基を有する単量体(a0)のカルボキシ基を構造(I)に変換することにより単量体(a1)を合成できる。
単量体(a0)としては、例えば(メタ)アクリル酸、クロトン酸、イソクロトン酸、マレイン酸、フマル酸、イタコン酸、マレイン酸モノメチル、フマル酸モノメチル等が挙げられる。
式(11)中、R7における炭素数1~9のアルキル基は、炭素数が9以下である以外は、R1における炭素数1~10のアルキル基と同様である。R8、R9はそれぞれR2、R3と同様である。
式(11)で表される化合物としては、例えば、アルキルビニルエーテル(例えば、エチルビニルエーテル、ブチルビニルエーテル、イソブチルビニルエーテル、t-ブチルビニルエーテル、2-エチルヘキシルビニルエーテル)、シクロアルキルビニルエーテル(例えば、シクロへキシルビニルエーテル)等のビニルエーテル類;エチル-1-プロペニルエーテル等の1-プロペニルエーテル類;エチル-1-ブテニルエーテル等の1-ブテニルエーテル類;等が挙げられる。これらのなかでは、ビニルエーテル類、1-プロペニルエーテル類が好ましい。
式(12)中、R10における炭素数1~9のアルキレン基は、炭素数が9以下である以外は、R4と同様である。
式(12)で表される化合物としては、例えば、2,3-ジヒドロフラン、5-メチル-2,3-ジヒドロフラン等のジヒドロフラン類;3,4-ジヒドロ-2H-ピラン、5,6-ジヒドロ-4-メトキシ-2H-ピラン等のジヒドロピラン類;等が挙げられる。
式(13)中、R11は、R5と同様である。R12は、炭素数が9以下である以外は、R6と同様である。
式(13)で表される化合物としては、例えば、1-メトキシ-1-シクロペンテン、1-メトキシ-1-シクロヘキセン、1-メトキシ-1-シクロヘプテン、1-エトキシ-1-シクロペンテン、1-エトキシ-1-シクロヘキセン、1-ブトキシ-1-シクロペンテン、1-ブトキシ-1-シクロヘキセン等の1-アルコキシ-1-シクロアルキレン類;1-エトキシ-3-メチル-1-シクロヘキセン等の置換基含有1-アルコキシ-1-シクロアルキレン類;等が挙げられる。
構成単位(A2)は、トリオルガノシリルオキシカルボニル基を有する。トリオルガノシリルオキシカルボニル基としては、例えば、下記式(II)で表される基が挙げられる。
-CO-O-SiR21R22R23 ・・・(II)
(式中、R21~R23はそれぞれ、炭素数1~20の炭化水素基を示す。)
シクロアルキル基、アリール基はそれぞれ、置換基を有していてもよい。置換基としては、例えばハロゲン原子、アルキル基、アシル基、ニトロ基、アミノ基等が挙げられる。置換基としてのアルキル基の炭素数は、1~18程度が好ましい。
R21~R23はそれぞれ同一でもよく異なってもよい。
安定したポリッシングレート(研磨速度)を示す塗膜が得られ、防汚性能を長期間安定して維持できる点で、R21~R23のうち少なくとも1つがイソプロピル基であることが好ましく、全てがイソプロピル基であることが特に好ましい。
単量体(a2)としては、トリオルガノシリルオキシカルボニル基とエチレン性不飽和結合とを有する単量体が挙げられる。
単量体(a2)は、共重合体(A-1)を有機溶剤に溶解したときの粘度が低くなる点から、エチレン性不飽和結合を1つ有する単官能単量体であることが好ましい。
CH2=C(R24)-CO-O-SiR21R22R23 ・・・(a2-1)
CH(COOR25)=C(R24)-CO-O-SiR21R22R23 ・・・(a2-2)
(式中、R21~R23は前記と同義であり、R24は水素原子またはメチル基を示し、R25はアルキル基を示す。)
トリメチルシリル(メタ)アクリレート、トリエチルシリル(メタ)アクリレート、トリ-n-プロピルシリル(メタ)アクリレート、トリ-n-ブチルシリル(メタ)アクリレート、トリ-n-アミルシリル(メタ)アクリレート、トリ-n-ヘキシルシリル(メタ)アクリレート、トリ-n-オクチルシリル(メタ)アクリレート、トリ-n-ドデシルシリル(メタ)アクリレート、トリフェニルシリル(メタ)アクリレート、トリ-p-メチルフェニルシリル(メタ)アクリレート、トリベンジルシリル(メタ)アクリレート、トリイソプロピルシリル(メタ)アクリレート、トリイソブチルシリル(メタ)アクリレート、トリ-s-ブチルシリル(メタ)アクリレート、トリ-2-メチルイソプロピルシリル(メタ)アクリレート、トリ-t-ブチルシリル(メタ)アクリレート、エチルジメチルシリル(メタ)アクリレート、n-ブチルジメチルシリル(メタ)アクリレート、ジイソプロピル-n-ブチルシリル(メタ)アクリレート、n-オクチルジ-n-ブチルシリル(メタ)アクリレート、ジイソプロピルステアリルシリル(メタ)アクリレート、ジシクロヘキシルフェニルシリル(メタ)アクリレート、t-ブチルジフェニルシリル(メタ)アクリレート、ラウリルジフェニルシリル(メタ)アクリレート等。
前記式(a2-2)で表される化合物の具体例として、以下に示すものが挙げられる。
トリイソプロピルシリルメチルマレート、トリイソプロピルシリルアミルマレート、トリ-n-ブチルシリル-n-ブチルマレート、t-ブチルジフェニルシリルメチルマレート、t-ブチルジフェニルシリル-n-ブチルマレート、トリイソプロピルシリルメチルフマレート、トリイソプロピルシリルアミルフマレート、トリ-n-ブチルシリル-n-ブチルフマレート、t-ブチルジフェニルシリルメチルフマレート、t-ブチルジフェニルシリル-n-ブチルフマレート等。
単量体(a2)は、市販品を購入することも可能であり、公知の方法を利用して適宜合成することも可能である。
構成単位(A3)は、下記式(4)又は(5)で表される構造からなる群から選ばれる少なくとも1種の構造(III)を有する。
-COO-M-OCO ・・・(4)
-COO-M-R32 ・・・(5)
(式中、MはZn、Cu、Mg又はCaを示し、R32は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。)
単量体(a1)~単量体(a3)はそれぞれマクロモノマー(b)に該当しない単量体である。
構成単位(B)は、マクロモノマー(b)由来の構成単位である。
マクロモノマー(b)は、ラジカル重合性基を有し、かつラジカル重合性基を有する単量体(以下「単量体(b1)」ともいう)由来の構成単位を2以上有する化合物である。マクロモノマー(b)が有する2以上の構成単位はそれぞれ同じでも異なってもよい。
ここで、Rは水素原子、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基又は非置換の若しくは置換基を有する複素環基を示す。
ここで、R51~R56はそれぞれ独立に、水素原子、アルキル基、脂環式基又はアリール基を示す。これらの基はそれぞれ、前記と同様のものが挙げられる。
前記置換基における-COOR51のR51としては、水素原子又はアルキル基が好ましい。すなわち、-COOR51は、カルボキシ基又はアルコキシカルボニル基が好ましい。アルコキシカルボニル基としては、例えば、メトキシカルボニル基が挙げられる。
前記置換基における-OR52のR52としては、水素原子又は非置換のアルキル基が好ましい。すなわち、-OR52は、ヒドロキシ基又はアルコキシ基が好ましい。アルコキシ基としては、例えば、炭素数1~12のアルコキシ基が挙げられ、具体例としては、メトキシ基が挙げられる。
前記置換基における-CONR55R56としては、例えば、カルバモイル基(-CONH2),N-メチルカルバモイル基(-CONHCH3)、N,N-ジメチルカルバモイル基(ジメチルアミド基:-CON(CH3)2)等が挙げられる。
前記置換基における親水性又はイオン性を示す基としては、例えば、カルボキシ基のアルカリ塩又はスルホキシ基のアルカリ塩、ポリエチレンオキシド基、ポリプロピレンオキシド基等のポリ(アルキレンオキシド)基及び四級アンモニウム塩基等のカチオン性置換基が挙げられる。
上記の中でも、入手のし易さから、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、t-ブチル基、ペンチル基、ヘキシル基、ヘプチル基及びオクチル基が好ましく、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、t-ブチル基、シクロプロピル基、シクロブチル基、イソボルニル基及びアダマンチル基が好ましい。
単量体(b1)としては、種々のものが用いられ得るが、例えば、
(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸イソアミル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸イソステアリル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸フェニル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸テトラヒドロフルフリル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸3,5,5-トリメチルシクロヘキシル、(メタ)アクリル酸ジシクロペンタニル、(メタ)アクリル酸ジシクロペンテニル、(メタ)アクリル酸ジシクロペンテニルオキシエチル、テルペンアクリレートやその誘導体、水添ロジンアクリレートやその誘導体、(メタ)アクリル酸ドコシル等の炭化水素基含有(メタ)アクリル酸エステル;
(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシブチル、(メタ)アクリル酸4-ヒドロキシブチル、グリセロール(メタ)アクリレート等の水酸基含有(メタ)アクリル酸エステル;
(メタ)アクリル酸、2-(メタ)アクリロイルオキシエチルヘキサヒドロフタル酸、2-(メタ)アクリロイルオキシプロピルヘキサヒドロフタル酸、2-(メタ)アクリロイルオキシエチルフタル酸、2-(メタ)アクリロイルオキシプロピルフタル酸、2-(メタ)アクリロイルオキシエチルマレイン酸、2-(メタ)アクリロイルオキシプロピルマレイン酸、2-(メタ)アクリロイルオキシエチルコハク酸、2-(メタ)アクリロイルオキシプロピルコハク酸、クロトン酸、フマル酸、マレイン酸、イタコン酸、シトラコン酸、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノオクチル、イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノブチル、イタコン酸モノオクチル、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノブチル、フマル酸モノオクチル、シトラコン酸モノエチル等のカルボキシル基含有ビニル系単量体;
無水マレイン酸、無水イタコン酸等の酸無水物基含有ビニル系単量体;
ジメチルマレート、ジブチルマレート、ジメチルフマレート、ジブチルフマレート、ジブチルイタコネート、ジパーフルオロシクロヘキシルフマレート等の不飽和ジカルボン酸ジエステル単量体;
(メタ)アクリル酸グリシジル、α-エチルアクリル酸グリシジル、(メタ)アクリル酸3,4-エポキシブチル等のエポキシ基含有ビニル系単量体;
ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート等のアミノ基含有(メタ)アクリル酸エステル系のビニル系単量体;
(メタ)アクリルアミド、N-t-ブチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-イソプロピルアクリルアミド、ヒドロキシエチルアクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、ダイアセトンアクリルアミド、マレイン酸アミド、マレイミド等のアミド基を含有するビニル系単量体;
スチレン、α-メチルスチレン、ビニルトルエン、(メタ)アクリロニトリル、塩化ビニル、酢酸ビニル、プロピオン酸ビニル等のビニル系単量体;
ジビニルベンゼン、エチレングリコールジ(メタ)アクリレート、1,3-ブチレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、アリル(メタ)アクリレート、トリアリルシアヌレート、マレイン酸ジアリル、ポリプロピレングリコールジアリルエーテル、N,N’-メチレンビス(メタ)アクリルアミド等の多官能性のビニル系単量体;
アクリロイルモルホリン、(メタ)アクリル酸ポリエチレングリコール、(メタ)アクリル酸ポリプロピレングリコール、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸n-ブトキシエチル、(メタ)アクリル酸イソブトキシエチル、(メタ)アクリル酸t-ブトキシエチル、(メタ)アクリル酸エトキシエトキシエチル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸ノニルフェノキシエチル、(メタ)アクリル酸3-メトキシブチル、(メタ)アクリル酸アセトキシエチル、「プラクセルFM」(ダイセル化学(株)製カプロラクトン付加モノマー、商品名)、「ブレンマーPME-100」(日油(株)製メトキシポリエチレングリコールメタクリレート(エチレングリコールの連鎖が2であるもの)、商品名)、「ブレンマーPME-200」(日油(株)製メトキシポリエチレングリコールメタクリレート(エチレングリコールの連鎖が4であるもの)、商品名)、「ブレンマーPME-400」(日油(株)製メトキシポリエチレングリコールメタクリレート(エチレングリコールの連鎖が9であるもの)、商品名)、「ブレンマー50POEP-800B」(日油(株)製オクトキシポリエチレングリコール-ポリプロピレングリコール-メタクリレート(エチレングリコールの連鎖が8であり、プロピレングリコールの連鎖が6であるもの)、商品名)及び「ブレンマー20ANEP-600」(日油(株)製ノニルフェノキシ(エチレングリコール-ポリプロピレングリコール)モノアクリレート、商品名)、「ブレンマーAME-100」(日油(株)製、商品名)、「ブレンマーAME-200」(日油(株)製、商品名)及び「ブレンマー50AOEP-800B」(日油(株)製、商品名)サイラプレーンFM-0711(JNC(株)製、商品名)、サイラプレーンFM-0721(JNC(株)製、商品名)、サイラプレーンFM-0725(JNC(株)製、商品名)、サイラプレーンTM-0701(JNC(株)製、商品名)、サイラプレーンTM-0701T(JNC(株)製、商品名)、X-22-174DX(信越化学工業(株)製、商品名)、X-22-2426(信越化学工業(株)製、商品名)、X-22-2475(信越化学工業(株)製、商品名)、
3-(メタ)アクリロキシプロピルトリメトキシシラン、3-(メタ)アクリロキシプロピルメチルジエトキシシラン、3-(メタ)アクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン等のシランカップリング剤含有モノマー、
前記単量体(a2)等の、シランカップリング剤含有モノマー以外のオルガノシリル基含有モノマー;
塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、クロロトリフルオロエチレン等のハロゲン化オレフィン、
(メタ)アクリル酸2-イソシアナトエチル2,2,2-トリフルオロエチル(メタ)アクリレート、2,2,3,3,3-ペンタフルオロフェニル(メタ)アクリレート、2-(パーフルオロブチル)エチル(メタ)アクリレート、3-(パーフルオロブチル)-2-ヒドロキシプロピル(メタ)アクリレート、2-(パーフルオロヘキシル)エチル(メタ)アクリレート、3-パーフルオロヘキシル-2-ヒドロキシプロピル(メタ)アクリレート、3-(パーフルオロ-3-メチルブチル)-2-ヒドロキシプロピル(メタ)アクリレート、2,2,3,3-テトラフルオロプロピル(メタ)アクリレート、1H,1H,5H-オクタフルオロペンチル(メタ)アクリレート、1H,1H,5H-オクタフルオロペンチル(メタ)メタクリレート、1H,1H,2H,2H-トリデカフルオロオクチル(メタ)アクリレート、1H-1-(トリフルオロメチル)トリフルオロエチル(メタ)アクリレート、1H,1H,3H-ヘキサフルオロブチル(メタ)アクリレート、1,2,2,2-テトラフルオロー1-(トリフルオロメチル)エチル(メタ)アクリレート等のフッ素含有モノマー(ただしハロゲン化オレフィンを除く)、
1-ブトキシエチル(メタ)アクリレート、1-(2-エチルへキシルオキシ)エチル(メタ)アクリレート、1-(シクロへキシルオキシ)エチルメタクリレート)、2-テトラヒドロピラニル(メタ)アクリレート等のアセタール構造を持つモノマー、
4-メタクリロイルオキシベンゾフェノン、(メタ)アクリル酸-2-イソシアナトエチル等が挙げられる。これらの単量体は1種を単独で用いてもよく2種以上を併用してもよい。
単量体(b1)の少なくとも一部は(メタ)アクリル系単量体であることが好ましい。
ヘテロアリール基としては、例えば、ピリジル基、カルバゾリル基等が挙げられる。
非芳香族の複素環式基としては、例えば、ピロリジニル基、ピロリドン基等が挙げられる。
アラルキル基としては、例えばベンジル基、フェニルエチル基等が挙げられる。
オルガノシリル基としては、例えばトリオルガノシリル基が挙げられる。トリオルガノシリル基としては、前記トリオルガノシリルオキシカルボニル基におけるトリオルガノシリル基(例えば-SiR21R22R23)が挙げられる。
カルボン酸エステル基としては、例えば前記Rの説明で挙げた-COOR51のR51がアルキル基、脂環式基又はアリール基である基が挙げられる。
アルコキシ基としては、前記-OR52のR52がアルキル基である基が挙げられる。
2級アミノ基としては、前記-NR53R54のR53が水素原子、R54がアルキル基、脂環式基又はアリール基である基が挙げられる。
3級アミノ基としては、前記-NR53R54のR53及びR54がそれぞれアルキル基、脂環式基又はアリール基である基が挙げられる。
アルキル基、アリール基、ハロゲン原子はそれぞれ前記と同様のものが挙げられる。
前記アリール基、ヘテロアリール基はそれぞれ置換基を有していてもよい。置換基としては、カルボン酸基、カルボン酸エステル基、エポキシ基、ヒドロキシ基、アルコキシ基、1級アミノ基、2級アミノ基、3級アミノ基、イソシアナト基、スルホン酸基、ハロゲン原子等が挙げられる。
カルボン酸エステル基、アルコキシ基、1級アミノ基、2級アミノ基、3級アミノ基、アルキル基、アリール基及びハロゲン原子はそれぞれ前記と同様のものが挙げられる。
オレフィン基としては、例えばアリル基等が挙げられる。オレフィン基は置換基を有していてもよい。オレフィン基における置換基としては、R48における置換基と同様のものが挙げられる。
置換又は非置換のアルキル(メタ)アクリレート[例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、i-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、i-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート、1-メチル-2-メトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、3-メチル-3-メトキシブチル(メタ)アクリレート]、置換又は非置換のアラルキル(メタ)アクリレート[例えば、ベンジル(メタ)アクリレート、m-メトキシフェニルエチル(メタ)アクリレート、p-メトキシフェニルエチル(メタ)アクリレート]、置換又は非置換のアリール(メタ)アクリレート[例えば、フェニル(メタ)アクリレート、m-メトキシフェニル(メタ)アクリレート、p-メトキシフェニル(メタ)アクリレート、o-メトキシフェニルエチル(メタ)アクリレート]、脂環式(メタ)アクリレート[例えば、イソボルニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート]、ハロゲン原子含有(メタ)アクリレート[例えば、トリフルオロエチル(メタ)アクリレート、パーフルオロオクチル(メタ)アクリレート、パーフルオロシクロヘキシル(メタ)アクリレート]等の疎水基含有(メタ)アクリル酸エステル単量体;
2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、2-ブトキシエチル(メタ)アクリレート、ブトキシジエチレングリコール(メタ)アクリレート、メトキシトリエチレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、2-(2-エチルヘキサオキシ)エチル(メタ)アクリレート等のオキシエチレン基含有(メタ)アクリル酸エステル単量体;
2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、グリセロール(メタ)アクリレート等の水酸基含有(メタ)アクリル酸エステル単量体;
メトキシポリエチレングリコールアリルエーテル、メトキシポリプロピレングリコールアリルエーテル、ブトキシポリエチレングリコールアリルエーテル、ブトキシポリプロピレングリコールアリルエーテル、メトキシポリエチレングリコール-ポリプロピレングリコールアリルエーテル、ブトキシポリエチレングリコール-ポリプロピレングリコールアリルエーテル等の末端アルコキシアリル化ポリエーテル単量体;
(メタ)アクリル酸グリシジル、α-エチルアクリル酸グリシジル、(メタ)アクリル酸3,4-エポキシブチル等のエポキシ基含有ビニル単量体;
ブチルアミノエチル(メタ)アクリレート、(メタ)アクリルアミド等の第一級または第二級アミノ基含有ビニル単量体;
ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート、ジメチルアミノブチル(メタ)アクリレート、ジブチルアミノエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリルアミド、ジメチルアミノプロピル(メタ)アクリルアミド等の第三級アミノ基含有ビニル単量体;
ビニルピロリドン、ビニルピリジン、ビニルカルバゾール等の複素環系塩基性単量体;
トリメチルシリル(メタ)アクリレート、トリエチルシリル(メタ)アクリレート、トリ-n-プロピルシリル(メタ)アクリレート、トリ-n-ブチルシリル(メタ)アクリレート、トリ-n-アミルシリル(メタ)アクリレート、トリ-n-ヘキシルシリル(メタ)アクリレート、トリ-n-オクチルシリル(メタ)アクリレート、トリ-n-ドデシルシリル(メタ)アクリレート、トリフェニルシリル(メタ)アクリレート、トリ-p-メチルフェニルシリル(メタ)アクリレート、トリベンジルシリル(メタ)アクリレート、トリイソプロピルシリル(メタ)アクリレート、トリイソブチルシリル(メタ)アクリレート、トリ-s-ブチルシリル(メタ)アクリレート、トリ-2-メチルイソプロピルシリル(メタ)アクリレート、トリ-t-ブチルシリル(メタ)アクリレート、エチルジメチルシリル(メタ)アクリレート、n-ブチルジメチルシリル(メタ)アクリレート、ジイソプロピル-n-ブチルシリル(メタ)アクリレート、n-オクチルジ-n-ブチルシリル(メタ)アクリレート、ジイソプロピルステアリルシリル(メタ)アクリレート、ジシクロヘキシルフェニルシリル(メタ)アクリレート、t-ブチルジフェニルシリル(メタ)アクリレート、ラウリルジフェニルシリル(メタ)アクリレート等のオルガノシリル基含有ビニル単量体;
メタクリル酸、アクリル酸、ビニル安息香酸、テトラヒドロフタル酸モノヒドロキシエチル(メタ)アクリレート、テトラヒドロフタル酸モノヒドロキシプロピル(メタ)アクリレート、テトラヒドロフタル酸モノヒドロキシブチル(メタ)アクリレート、フタル酸モノヒドロキシエチル(メタ)アクリレート、フタル酸モノヒドロキシプロピル(メタ)アクリレート、コハク酸モノヒドロキシエチル(メタ)アクリレート、コハク酸モノヒドロキシプロピル(メタ)アクリレート、マレイン酸モノヒドロキシエチル(メタ)アクリレート、マレイン酸モノヒドロキシプロピル(メタ)アクリレート等のカルボキシ基含有エチレン性不飽和単量体;
アクリロニトリル、メタクリロニトニル等のシアノ基含有ビニル単量体;
アルキルビニルエーテル[例えば、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、ヘキシルビニルエーテル、2-エチルヘキシルビニルエーテル等]、シクロアルキルビニルエーテル[例えば、シクロヘキシルビニルエーテル等]等のビニルエーテル単量体;
酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等のビニルエステル単量体;
スチレン、ビニルトルエン、α-メチルスチレン等の芳香族ビニル単量体;
塩化ビニル、フッ化ビニル等のハロゲン化オレフィン;等。
他の構成単位の好ましい具体例として、以下の単量体由来の構成単位が挙げられる。
トリイソプロピルシリルメチルマレート、トリイソプロピルシリルアミルマレート、トリ-n-ブチルシリル-n-ブチルマレート、t-ブチルジフェニルシリルメチルマレート、t-ブチルジフェニルシリル-n-ブチルマレート、トリイソプロピルシリルメチルフマレート、トリイソプロピルシリルアミルフマレート、トリ-n-ブチルシリル-n-ブチルフマレート、t-ブチルジフェニルシリルメチルフマレート、t-ブチルジフェニルシリル-n-ブチルフマレート等のオルガノシリル基含有ビニル単量体;
無水マレイン酸、無水イタコン酸等の酸無水物基含有ビニル単量体;
クロトン酸、フマル酸、イタコン酸、マレイン酸、シトラコン酸、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノブチル、マレイン酸モノオクチル、イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノブチル、イタコン酸モノオクチル、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノブチル、フマル酸モノオクチル、シトラコン酸モノエチル等のカルボキシ基含有エチレン性不飽和単量体;
ジメチルマレート、ジブチルマレート、ジメチルフマレート、ジブチルフマレート、ジブチルイタコネート、ジパーフルオロシクロヘキシルフマレート等の不飽和ジカルボン酸ジエステル単量体;
塩化ビニリデン、フッ化ビニリデン、クロロトリフルオロエチレン等のハロゲン化オレフィン;
エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、アリルメタクリレート、トリアリルシアヌレート、マレイン酸ジアリル、ポリプロピレングリコールジアリルエーテル等の多官能単量体等。
Qに含まれる2以上の構成単位(b’)はそれぞれ、同じでもよく異なってもよい。
Qは、構成単位(b’)のみからなるものでもよく、構成単位(b’)以外の他の構成単位をさらに含むものであってもよい。
Qを構成する構成単位の数は、マクロモノマー(b)の数平均分子量が後述する好ましい範囲内となる値が好ましい。
Eとしては、例えば、公知のラジカル重合で得られるポリマーの末端基と同様に、水素原子、ラジカル重合開始剤に由来する基、ラジカル重合性基等が挙げられる。
マクロモノマー(b)の数平均分子量は、ゲルろ過クロマトグラフィー(GPC)により、ポリスチレンを基準物質として測定される。
マクロモノマー(b)の数平均分子量は、マクロモノマー(b)製造時における重合開始剤や連鎖移動剤の使用量等によって調整できる。
マクロモノマー(b)のガラス転移温度は、示差走査熱量計(DSC)で測定することができる。
マクロモノマー(b)のガラス転移温度は、マクロモノマー(b)を形成する単量体の組成等によって調整できる。
マクロモノマー(b)の製造方法としては、例えば、コバルト連鎖移動剤を用いて製造する方法、α-メチルスチレンダイマー等のα置換不飽和化合物を連鎖移動剤として用いる方法、重合体にラジカル重合性基を化学的に結合させる方法、熱分解による方法等が挙げられる。
これらの中で、マクロモノマー(b)の製造方法としては、製造工程数が少なく、連鎖移動定数の高い触媒を使用する点で、コバルト連鎖移動剤を用いて製造する方法が好ましい。なお、コバルト連鎖移動剤を用いて製造した場合のマクロモノマー(b)は、前記式(b-1)で表される構造を有する。
重合体にラジカル重合性基を化学的に結合させる方法としては、例えば、ハロゲン基を有する重合体のハロゲン基を、ラジカル重合性の炭素-炭素二重結合を有する化合物で置換することにより製造する方法、酸基を有するビニル系単量体とエポキシ基を有するビニル系重合体とを反応させる方法、エポキシ基を有するビニル系重合体と酸基を有するビニル系単量体とを反応させる方法、水酸基を有するビニル系重合体とジイソシアネート化合物とを反応させ、イソシアネート基を有するビニル系重合体を得て、このビニル系重合体と水酸基を有するビニル系単量体とを反応させる方法等が挙げられ、いずれの方法によって製造されても構わない。
構成単位(C)としては、特に限定されず、例えば、単量体(a1)、単量体(a2)、単量体(a3)及びマクロモノマー(b)以外の他の単量体(c)単位が挙げられる。
単量体(c)としては、単量体(a1)、単量体(a2)、マクロモノマー(b)と共重合可能なものであれば特に限定されず、エチレン性不飽和結合等のラジカル重合性基を有する種々の単量体を用いることができる。例えば前記で挙げたマクロモノマー(b)を得るための単量体(b1)と同様のものを用いることができる(ただし、単量体(a1)、単量体(a2)及び単量体(a3)は除く。)。単量体(c)は1種又は2種以上を必要に応じて適宜選択して使用することができる。
疎水基含有(メタ)アクリル酸エステル単量体としては、例えば、置換又は未置換のアルキル(メタ)アクリレート[例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、i-プロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、i-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート、1-メチル-2-メトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、3-メチル-3-メトキシブチル(メタ)アクリレート]、置換又は未置換のアラルキル(メタ)アクリレート[例えば、ベンジル(メタ)アクリレート、m-メトキシフェニルエチル(メタ)アクリレート、p-メトキシフェニルエチル(メタ)アクリレート]、置換又は未置換のアリール(メタ)アクリレート[例えば、フェニル(メタ)アクリレート、m-メトキシフェニル(メタ)アクリレート、p-メトキシフェニル(メタ)アクリレート、o-メトキシフェニルエチル(メタ)アクリレート]、脂環式(メタ)アクリレート[例えば、イソボルニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート]、トリフルオロエチル(メタ)アクリレート、パーフルオロオクチル(メタ)アクリレート、パーフルオロシクロヘキシル(メタ)アクリレート等が挙げられ、アルキル(メタ)アクリレートが好ましい。
オキシエチレン基含有(メタ)アクリル酸エステル単量体としては、下記式(c-1)で表される単量体が好ましい。
Z1-(CH2CH2O)pR57 (c-1)
(式中、Z1は(メタ)アクリロイルオキシ基を示し、R57は水素原子、炭素数1~10のアルキル基、又はアリール基を示し、pは1~15の整数を示す。)
R57における炭素数1~10のアルキル基、アリール基はそれぞれ前記R3で挙げたものと同様のものが挙げられる。
pは、耐水性、耐クラック性の点から、1~10の整数が好ましく、1~5の整数がより好ましく、1~3の整数がさらに好ましく、1又は2が特に好ましい。
単量体(c)は、市販品を購入することも可能であり、公知の方法を利用して適宜合成することも可能である。
共重合体(A-1)における構成単位(A1)及び構成単位(A2)の合計の含有量(いずれか一方の構成単位を含まない場合を含む。)は、全構成単位の合計(100質量%)に対し、1~80質量%が好ましく、10~70質量%がより好ましく、20~60質量%がさらに好ましい。構成単位(A1)及び構成単位(A2)の合計の含有量が前記範囲の下限値以上であれば、形成される塗膜の自己研磨性がより優れる。構成単位(A1)及び構成単位(A2)の合計の含有量が前記範囲の上限値以下であれば、形成される塗膜が適度な加水分解性を有し、長期にわたって自己研磨性が維持され、防汚効果がより優れたものとなる。
共重合体中の各構成単位の含有量(質量%)は、ガスクロマトグラフィー、高速液体クロマトグラフィー、核磁気共鳴スペクトル法等の公知の方法により測定できる。
前記単量体混合物は、単量体(a’)1~80質量%と、マクロモノマー(b)1~60質量%と、単量体(c)0~98質量%とからなることが好ましい。各単量体の含有量は、単量体混合物全量に対する割合である。各単量体のより好ましい含有量の範囲は、各単量体由来の構成単位の好ましい含有量の範囲と同様である。
共重合体(A-1)の重量平均分子量が前記範囲の上限値以下であれば、共重合体(A-1)を有機溶剤に溶解した溶液の粘度がより低くなり、この溶液を含む防汚塗料組成物として高固形分低粘度のものを得やすい。共重合体(A-1)の重量平均分子量が前記範囲の下限値以上であれば、形成される塗膜の硬度、耐久性等がより優れる。
重量平均分子量及び数平均分子量はそれぞれ、ゲルろ過クロマトグラフィー(GPC)により、ポリスチレンを基準物質として測定される。
酸価は、水酸化カリウム溶液による中和滴定により測定される。
共重合体(A-1)の製造方法としては、例えば、以下の製造方法(α)が挙げられる。
製造方法(α):単量体(a1)及び単量体(a2)からなる群から選ばれる少なくとも1種の単量体(a’)と、マクロモノマー(b)とを含む単量体混合物(α1)を重合する方法。
前記単量体混合物(α1)は、単量体(a3)、他の単量体(c)をさらに含んでもよい。
製造方法(β):エチレン性不飽和結合及びカルボキシ基を有する単量体(a0)と、マクロモノマー(b)とを含む単量体混合物(β1)を重合し、カルボキシ基を有する共重合体(A0)を得て、この共重合体(A0)のカルボキシ基を構造(I)に変換する方法。
単量体混合物(β1)は、単量体(a2)、単量体(a3)、他の単量体(c)をさらに含んでもよい。
製造方法(α)において、単量体混合物(α1)の組成、すなわち単量体混合物(α1)を構成する単量体の種類及び全単量体の合計質量に対する各単量体の含有量(質量%)は、共重合体(A-1)の組成、すなわち共重合体(A-1)を構成する各単量体由来の構成単位の種類及び全構成単位の合計質量に対する各構成単位の含有量(質量%)と同様である。
単量体混合物(α1)の重合は、後述する第六の態様の(メタ)アクリル系共重合体の製造方法における単量体混合物の重合と同様にして行うことができる。
製造方法(β)において、単量体混合物(β1)の組成は、単量体(a1)が単量体(a0)である以外は、共重合体(A-1)の組成と同様である。単量体(a0)は前記単量体(a1)の説明で挙げたものと同様である。単量体混合物(β1)の重合は、製造方法(α)における単量体混合物(α1)の重合と同様にして行うことができる。
アルケニル化合物としては前記と同様のものが挙げられる。
共重合体(A0)と1-アルケニルエーテルとの反応は、前記単量体(a0)とアルケニル化合物との反応と同様にして行うことができる。
共重合体(A-1)は、構成単位(A1)及び構成単位(A2)からなる群から選ばれる少なくとも1種の構成単位を有するため、海水中等で加水分解可能である。そのため共重合体(A-1)を含む塗膜は、海水中等で自己研磨性を示す。すなわち、共重合体(A-1)は、構造(I)及びトリオルガノシリルオキシカルボニル基のいずれか一方又は両方を有しており、この状態では海水に溶解しないが、海水との接触により構造(I)やトリオルガノシリルオキシカルボニル基が加水分解すると、カルボキシ基等が生成し、海水に溶解する。塗膜表面が徐々に海水に溶解して表面更新(自己研磨)される。したがって、共重合体(A-1)を含む防汚塗料組成物の塗膜も自己研磨性を示す。この塗膜は海水中で表面更新され、防汚性を示す。特に塗膜が防汚剤を含む場合は、塗膜表面に常に防汚剤が露出し、優れた防汚効果が長期にわたって発揮される。
従来、防汚塗料組成物を高固形分低粘度にしようとすると、塗膜の硬度が低下する傾向があった。防汚塗料組成物に共重合体(A-1)を用いることで、防汚塗料組成物を高固形分低粘度にした場合でも、硬度に優れた塗膜を形成できる。
また、共重合体(A-1)にあっては、共重合体(A-1)を含む塗料を塗装し塗膜を形成した後、塗装直後からの塗膜の硬度の上昇速度が速く、耐盤木性が高い傾向がある。この上昇速度が遅いと、塗膜の硬度が充分に高くなるのに時間がかかる。塗膜の硬度が充分に高くなる前に塗装物を移動させたりすると、塗膜が変形して外観等が悪化するため、塗装後に次の工程を進めるまでに時間がかかる。塗膜の硬度の上昇速度が速いことは、生産性の点で好ましい。
本発明の第二の態様は、構成単位(A3)と構成単位(B)とを有する(メタ)アクリル系共重合体(以下、「共重合体(A-2)」ともいう。)と、有機溶剤と、を含み、25℃における粘度が5×104mPa・s以下である重合体溶液である。
重合体溶液においては、有機溶剤中に重合体が溶解している。
共重合体(A-2)は、構成単位(A1)、構成単位(A2)、構成単位(C)をさらに有することができる。
構成単位(B)、構成単位(A1)、構成単位(A2)、構成単位(C)はそれぞれ前記と同様である。
構成単位(A3)は、下記式(4)又は(5)で表される構造からなる群から選ばれる少なくとも1種の構造(III)を有する。
-COO-M-OCO ・・・(4)
-COO-M-R32 ・・・(5)
(式中、MはZn、Cu、Mg又はCaを示し、R32は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。)
R32の有機酸残基は、有機酸からプロトン1つを除いた残りの部分(例えばカルボン酸のカルボキシ基からプロトンを除いた残りの部分)をいい、このプロトンの代わりにMとイオン結合している。
有機酸としては、カルボン酸が好ましく、例えばモノクロル酢酸、モノフルオロ酢酸、酢酸、プロピオン酸、オクチル酸、バーサチック酸、イソステアリン酸、パルミチン酸、クレソチン酸、α-ナフトエ酸、β-ナフトエ酸、安息香酸、2,4,5-トリクロロフェノキシ酢酸、2,4-ジクロロフェノキシ酢酸、キノリンカルボン酸、ニトロ安息香酸、ニトロナフタレンカルボン酸、ピルビン酸、ナフテン酸、アビエチン酸、水添アビエチン酸等のモノカルボン酸等が挙げられる。
R32としては、長期にわたりクラックや剥離を防止できる耐久性の高い塗膜が得られる点で、炭素数1~20の脂肪酸残基(脂肪族モノカルボン酸残基)が好ましい。
構造(III)を有する単量体(a3)としては、例えば、式(4)で表される基の両末端に、非置換又は置換基を有するビニル基が結合した単量体、式(5)で表される基の片末端(R32側とは反対側)に、非置換又は置換基を有するビニル基が結合した単量体等が挙げられる。
式(4)で表される基の両末端に前記ビニル基が結合した単量体として、例えば下記式(a3-1)で表される単量体(以下、「単量体(a3-1)」ともいう。)が挙げられる。
式(5)で表される基の片末端に前記ビニル基が結合した単量体として、例えば下記式(a3-2)で表される単量体(以下、「単量体(a3-2)」ともいう。)が挙げられる。
CH2=C(R31)-CO-O-M-R32 ・・・(a3-2)
式中、MはZn、Cu、Mg又はCaを示し、R31は水素原子又はメチル基を示し、R32は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。
M及びR32はそれぞれ前記と同様であり、好ましい態様も同様である。
中でも、共重合体(A-2)の透明性が高くなり、これを含む塗膜の色調が美しくなる傾向にある点から、(メタ)アクリル酸亜鉛、(メタ)アクリル酸銅が好ましい。
中でも、共重合体(A-2)の透明性が高くなり、これを含む塗膜の色調が美しくなる傾向にある点から、MがZnである亜鉛含有モノマーが好ましい。さらに、得られる塗膜の耐久性の点から、脂肪酸亜鉛(メタ)アクリレート(式(a3-2)中のMがZn、R22が脂肪酸残基であるもの)、又は脂肪酸銅(メタ)アクリレート(式(a3-2)中のMがCu、R22が脂肪酸残基であるもの)がより好ましい。
単量体(a3-1)と単量体(a3-2)との組み合わせとしては、(メタ)アクリル酸亜鉛と脂肪酸亜鉛(メタ)アクリレートとの組み合わせ、又は(メタ)アクリル酸銅と脂肪酸銅(メタ)アクリレートが好ましい。
単量体(a3-1)は、例えば、式(a3-1)中のMに対応する金属元素を含む無機金属化合物と、(メタ)アクリル酸とを、有機溶剤等の希釈剤またはエチレン性不飽和単量体等の重合性不飽和基を有する反応性希釈剤中で反応させる方法により得られる。この方法で得られる金属含有重合性単量体を含有する混合物は、有機溶剤や他の単量体との相溶性に優れ、重合を容易に行うことができる。前記反応は、水の存在下で行うことが好ましく、反応物中の水の含有量を0.01~30質量%の範囲とすることが好ましい。前記無機金属化合物としては、例えばZn、Cu、Mg及びCaから選ばれる金属の酸化物、水酸化物、塩化物等が挙げられる。
その際、R22に対応する有機酸の使用量は、無機金属化合物に対して0.01~3倍モルであることが好ましく、0.01~0.95倍モルがより好ましく、0.1~0.7倍モルがさらに好ましい。この有機酸の含有量が0.01倍モル以上であると、この単量体混合物の製造工程において固体の析出が抑制されると共に、得られる塗膜の自己研磨性、耐クラック性がより良好となる。3倍モル以下であると、得られる塗膜の防汚性がより長期間維持される傾向にある。
共重合体(A-2)における構成単位(A3)の含有量は、全構成単位の合計(100質量%)に対し、1~40質量%が好ましく、5~30質量%がより好ましい。構成単位(A3)の含有量が前記範囲の下限値以上であれば、形成される塗膜の自己研磨性がより優れる。構成単位(A3)の含有量が前記範囲の上限値以下であれば、重合体溶液やこれを含む重合体組成物、防汚塗料組成物等の貯蔵安定性、形成される塗膜の密着性、海水中での耐水性、及び硬度と耐クラック性のバランスが向上する傾向にある。
前記単量体混合物は、単量体(a3)1~40質量%と、マクロモノマー(b)1~60質量%と、単量体(c)10~98質量%とからなることが好ましい。各単量体の含有量は、単量体混合物全量に対する割合である。各単量体のより好ましい含有量の範囲は、各単量体由来の構成単位の好ましい含有量の範囲と同様である。
共重合体(A-2)の重量平均分子量が前記範囲の上限値以下であれば、塗膜の硬度がより優れる。また、重合体溶液やこれを含む重合体組成物、防汚塗料組成物等を高固形分でも低粘度のものを得やすい。また、形成される塗膜の防汚性が優れる。共重合体(A-2)の重量平均分子量が前記範囲の下限値以上であれば、形成される塗膜の硬度、耐久性がより優れる。
共重合体(A-2)の多分散度(Mw/Mn)は、1.5~5.0が好ましく、2.2~3.0がより好ましい。
共重合体(A-2)の酸価は、水酸化カリウム溶液による中和滴定等公知の手法により測定される。
本態様の重合体溶液中の共重合体(A-2)の含有量は、重合体溶液の全量に対し、85質量%以下であることが好ましく、10~80質量%がより好ましく、30~75質量%がさらに好ましく、55~75質量%が特に好ましい。共重合体(A-2)の含有量が前記上限値以下であれば、耐水性、塗膜硬度等に優れる塗膜を得やすい傾向がある。共重合体(A-2)の含有量が前記下限値以上であれば、VOC含有量の少ない防汚塗料組成物を容易に得ることができる。
有機溶剤としては、共重合体(A-2)を溶解できるものであれば特に限定されず、例えばメチルアルコール、エチルアルコール、イソプロピルアルコール等の一価アルコール系溶剤;エチレングリコール、1,2-プロピレングリコール等の多価アルコール系溶剤;アセトン、メチルエチルケトン、アセチルアセトン、メチルイソブチルケトン等のケトン系溶剤;メチルエチルエーテル、ジオキサン等のエーテル系溶剤;エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノn-プロピルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノプロピルエーテル等のグリコールエーテル系溶剤;エチレングリコールモノアセテート、エチレングリコールジアセテート、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のグリコールアセテート系溶剤;酢酸n-ブチル、エチル3-エトキシプロピオネート等の他のエステル系溶剤;n-ペンタン、n-ヘキサン等の脂肪族系炭化水素系溶剤;トルエン、キシレン、ソルベントナフサ等の芳香族系炭化水素系溶剤;等が挙げられる。これらの有機溶剤はいずれか1種を単独で、または2種以上を組合わせて用いることができる。
本態様の重合体溶液は、共重合体(A-2)及び有機溶剤以外の他の成分をさらに含んでもよい。
他の成分としては、例えば、後述する防汚塗料組成物における他の成分と同様のものが挙げられる。
他の成分の含有量は、共重合体(A-2)(100質量%)に対して200質量%以下が好ましく、0質量%であってもよい。
本態様の重合体溶液の25℃における粘度は、5×104mPa・s以下であり、5000mPa・s以下が好ましく、5000mPa・s未満がより好ましく、4000mPa・s未満がさらに好ましく、3000mPa・s未満がさらに好ましく、2,000mPa・s未満がさらに好ましく、1,000mPa・s未満が特に好ましい。重合体溶液の粘度が前記上限値以下であれば、重合体溶液やこれを含む重合体組成物に希釈のための有機溶剤を加えなくても、防汚剤等の配合や塗装を行うことができ、VOC含有量の少ない防汚塗料組成物が得られる。
本態様の重合体溶液は、少なくとも固形分55質量%での粘度が上記の好ましい上限値以下であることが好ましい。
重合体溶液の粘度の下限は特に限定されないが、塗装時の塗料タレ抑制の点では、100mPa・s以上が好ましい。
したがって、重合体溶液の25℃における粘度は、100~5×104mPa・sが好ましく、100~5000mPa・sがより好ましく、100mPa・s以上5,000mPa・s未満がさらに好ましく、100mPa・s以上4,000mPa・s未満がさらに好ましく、100mPa・s以上3,000mPa・s未満がさらに好ましく、100mPa・s以上2,000mPa・s未満がさらに好ましく、100mPa・s以上1,000mPa・s未満が特に好ましい。
比(VX)=粘度(VB)/固形分量(NV) ・・・(i)
粘度(VB)は、試料(重合体溶液)の25℃においてB型粘度計で測定される粘度(mPa・s)を示し、固形分量(NV)は試料の加熱残分(質量%)を示す。例えば粘度(VB)が600mPa・s、固形分量(NV)が60質量%の場合は、比(VX)は10である。試料の固形分量(加熱残分)は、後述する実施例に記載の方法により測定される。
比(VX)が前記上限値以下であれば、重合体溶液やこれを含む重合体組成物に希釈のための有機溶剤を加えなくても、防汚剤等を配合したり塗装したりすることができ、VOC含有量の少ない防汚塗料組成物が得られる。
本態様の重合体溶液の製造方法としては、例えば、以下の製造方法(γ)又は(δ)により共重合体(A-2)を製造し、必要に応じて有機溶剤を添加する方法が挙げられる。これらのうち、耐水性の点では、製造方法(γ)により共重合体(A-2)を製造し、必要に応じて有機溶剤を添加する方法が好ましい。
製造方法(γ):単量体(a3)とマクロモノマー(b)とを含む単量体混合物(γ1)を重合する方法。
製造方法(δ):エチレン性不飽和結合及びカルボキシ基を有する単量体(a0)と、マクロモノマー(b)とを含む単量体混合物(δ1)を重合し、カルボキシ基を有する共重合体(A0’)を得て、この共重合体(A0’)のカルボキシ基を構造(III)に変換する方法。
単量体混合物(γ1)の重合は、後述する第六の態様の(メタ)アクリル系共重合体の製造方法における単量体混合物の重合と同様にして行うことができる。
単量体混合物(γ1)の重合により得られた重合生成物が有機溶剤を含み、25℃における粘度が前記の上限値以下である場合は、この重合生成物をそのまま本態様の重合体溶液とすることができる。粘度の低減、ハンドリング性の向上等のために、さらなる有機溶剤を添加してもよい。
重合生成物が有機溶剤を含み、25℃における粘度が前記の上限値以下である場合以外の場合には、重合生成物または重合生成物から回収しした共重合体(A-2)に、有機溶剤を加えて本態様の重合体溶液を得る。
単量体混合物(δ1)の重合は、後述する第六の態様の(メタ)アクリル系共重合体の製造方法における単量体混合物の重合と同様にして行うことができる。
共重合体(A0’)のカルボキシ基を構造(III)に変換する方法としては、例えば、共重合体(A0’)と、酢酸銅、酢酸亜鉛等の有機酸金属塩とを反応させる方法が挙げられる。有機酸金属塩の金属は前記Mに対応する。
共重合体(A0’)と有機酸金属塩との反応は、例えば還流温度まで昇温し、留出する酢酸等の有機酸、水及び有機溶剤の混合液を除去しつつ、同量の有機溶剤をを補充しながら、反応を10~20時間継続すること等で行うことができる。
製造方法(ε):有機溶剤中で、単量体(a3)とマクロモノマー(b)とを含む単量体混合物(ε1)を重合し、重合生成物として、または前記重合により得られる重合生成物を有機溶剤で希釈して、本態様の重合体溶液を得る方法。
単量体混合物(ε1)は、単量体(a1)、単量体(a2)、単量体(c)をさらに含んでもよい。単量体混合物(ε1)の組成は、共重合体(A-2)の組成と同様である。
単量体混合物(ε1)の重合は、有機溶剤中で行う(つまり溶液重合法により行う)ことが必須である以外は、後述する第六の態様の(メタ)アクリル系共重合体の製造方法における単量体混合物の重合と同様にして行うことができる。
反応系全体とは、共重合に用いられるすべての材料(各種単量体、有機溶剤、必要に応じて用いられるラジカル重合開始剤、連鎖移動剤等)の合計である。
この場合、反応系から全単量体を除いた全量に対する有機溶剤の割合は、重合体溶液から共重合体(A-2)を除いた全量に対する有機溶剤の含有量よりも低い。反応系から全単量体を除いた全量に対する有機溶剤の割合の下限は特に限定されないが、重合中の溶液粘度が低い方が重合安定性が良好であることから、20質量%以上が好ましい。
共重合体(A-2)は、構成単位(A3)を有するため、海水中等で加水分解可能である。そのため、共重合体(A-2)を含む塗膜は、海水中等で自己研磨性を示す。すなわち、共重合体(A-2)は、-CO-O-M-O-CO-構造及び-CO-O-M-R32構造のいずれか一方又は両方を有しており、この状態では海水に溶解しないが、海水との接触によりこの構造が加水分解すると、カルボキシ基等が生成し、海水に溶解する。塗膜表面が徐々に海水に溶解して表面更新(自己研磨)される。したがって、本態様の重合体溶液を含む重合体含有組成物やこれを含む防汚塗料組成物の塗膜も自己研磨性を示す。この塗膜は海水中で表面更新され、防汚性を示す。特に塗膜が防汚剤を含む場合は、塗膜表面に常に防汚剤が露出し、優れた防汚効果が長期にわたって発揮される。
従来、防汚塗料組成物を高固形分低粘度にしようとすると、塗膜の硬度が低下する傾向があった。防汚塗料組成物に本態様の重合体溶液を用いることで、防汚塗料組成物を高固形分低粘度にした場合でも、硬度に優れた塗膜を形成できる。
また、本態様の重合体溶液にあっては、この重合体溶液を含む塗料を塗装し塗膜を形成した際、塗装直後からの塗膜の硬度の上昇速度が速く、耐盤木性が高い傾向がある。この上昇速度が遅いと、塗膜の硬度が充分に高くなるのに時間がかかる。塗膜の硬度が充分に高くなる前に塗装物を移動させたりすると、塗膜が変形して外観等が悪化するため、塗装後に次の工程を進めるまでに時間がかかる。塗膜の硬度の上昇速度が速いことは、生産性の点で好ましい。
本発明の第三の態様は、第一の態様の共重合体(A-1)を含む重合体含有組成物(以下、「組成物(B-1)」ともいう。)である。
本発明の第四の態様は、第二の態様の重合体溶液を含む重合体含有組成物(以下、「組成物(B-2)」ともいう。)である。
組成物(B-1)に含まれる共重合体(A-1)は1種でもよく2種以上でもよい。
組成物(B-1)中の共重合体(A-1)の含有量は、組成物(B-1)の総質量に対して50質量%以上が好ましく、57質量%以上がより好ましく、59質量%以上がさらに好ましい。共重合体(A-1)の含有量が前記下限値以上であれば、相対的に組成物(B-1)中に含まれ得る有機溶剤の含有量が少なくなり、VOC含有量の少ない防汚塗料組成物を容易に得ることができる。
共重合体(A-1)の含有量の上限は、特に限定されず、100質量%であってもよい。組成物(B-1)が有機溶剤を含む場合は、組成物(B-1)の25℃における粘度が5×104以下となる量が好ましく、共重合体(A-1)の重量平均分子量、ガラス転移温度、架橋構造の有無等によっても異なるが、80質量%以下が好ましく、85質量%以下がより好ましい。
組成物(B-1)は、有機溶剤をさらに含むことが好ましい。組成物(B-1)が有機溶剤を含むと、組成物(B-1)を含む防汚塗料組成物の塗工適性、形成される塗膜の耐水性、成膜性等がより優れる。
有機溶剤としては、共重合体(A-1)を溶解できるものであれば特に限定されず、例えばトルエン、キシレン等の炭化水素系溶剤;1-アルケニルエーテル等のエーテル系溶剤;メチルイソブチルケトン等のケトン系溶剤;酢酸n-ブチル、プロピレングリコールモノメチルエーテルアセテート、エチル3-エトキシプロピオネート等のエステル系溶剤;等が挙げられる。これらはいずれか1種を単独で、又は2種以上を組合わせて用いることができる。
アルケニル化合物としては、前記で挙げたものと同様のものが挙げられる。アルケニル化合物は、1種を単独で、又は2種以上を組合わせて用いることができる。
アルケニル化合物としては、前記で挙げたもののなかでも、貯蔵安定性の向上効果がより優れる点で、ブチルビニルエーテルやイソブチルビニルエーテル等のビニルエーテル類が好ましい。
1-アルケニルエーテルと他の有機溶剤とを併用してもよい。
有機溶剤の含有量は、組成物(B-1)の25℃における粘度が5×104以下となる量が好ましく、共重合体(A-1)の重量平均分子量、ガラス転移温度、架橋構造の有無等によっても異なるが、30質量%以上が好ましく、25質量%以上がより好ましい。
組成物(B-1)は、共重合体(A-1)及び有機溶剤以外の他の成分をさらに含んでもよい。
他の成分としては、例えば、後述する防汚塗料組成物における他の成分と同様のものが挙げられる。
他の成分の含有量は、共重合体(A-1)(100質量%)に対して300質量%以下が好ましく、0質量%であってもよい。
組成物(B-1)が有機溶剤を含む場合、組成物(B-1)の25℃における粘度は、5×104mPa・s以下が好ましい。より好ましい粘度は第二の態様の重合体溶液の25℃における粘度と同様である。
組成物(B-1)は、少なくとも固形分55質量%での粘度が上記の好ましい上限値以下であることが好ましい。
比(VX)は、前記式(i)において、重合体溶液の粘度、固形分量をそれぞれ組成物(B-1)の粘度、固形分量に置き換えて算出される。
組成物(B-1)は、防汚塗料組成物のほか、防曇塗料組成物等に用いることもできる。
組成物(B-2)は、第二の態様の重合体溶液を含む。したがって、共重合体(A-2)と有機溶剤とを含む。
組成物(B-2)は、第二の態様の重合体溶液のみからなるものであってもよく、第二の態様の重合体溶液に加えて他の材料をさらに含むものであってもよい。
他の材料としては、例えば、希釈用の有機溶剤、他の成分等が挙げられる。希釈用の有機溶剤としては、重合体溶液の有機溶剤として挙げたものと同様のものが挙げられる。重合体溶液中の有機溶剤と希釈用の有機溶剤とは同じでもよく異なってもよい。他の成分は前記と同様である。
有機溶剤の含有量の上限は特に限定されないが、例えば、共重合体(A-2)に対して100質量%以下とすることができる。有機溶剤の含有量が前記範囲の上限値以下であれば、VOC含有量の少ない防汚塗料組成物が得られる。
この有機溶剤の含有量は、組成物(B-2)に含まれる全ての有機溶剤の総量である。
組成物(B-2)は、防汚塗料組成物のほか、防曇塗料組成物等に用いることもできる。
組成物(B-3)における有機溶剤の含有量は、共重合体(A-2)に対して45質量%以上が好ましく、50質量%以上がより好ましい。
有機溶剤の含有量の上限は特に限定されず、例えば前記組成物(B-2)と同様であってよい。
組成物(B-3)は、第二の態様の重合体溶液のみからなるものであってもよく、第二の態様の重合体溶液に加えて他の材料をさらに含むものであってもよい。
他の材料としては、例えば、希釈用の有機溶剤、他の成分等が挙げられる。これらはそれぞれ前記と同様のものが挙げられる。
組成物(B-3)の水分含有量は、15質量%以下が好ましく、10質量%以下がより好ましい。下限は特に限定されず、0質量%であってもよい。
組成物(B-3)は、組成物(B-2)と同様にして調製できる。
組成物(B-3)は、そのまま、又は必要に応じて防汚剤等と混合して、防汚塗料組成物とすることができる。
組成物(B-3)は、防汚塗料組成物のほか、防曇塗料組成物等に用いることもできる。
本発明の第五の態様は、組成物(B-1)又は組成物(B-2)を含む防汚塗料組成物である。
防汚塗料組成物が組成物(B-1)を含む場合、防汚塗料組成物は少なくとも共重合体(A-1)を含む。防汚塗料組成物が組成物(B-2)を含む場合、防汚塗料組成物は少なくとも共重合体(A-2)及び有機溶剤を含む。
防汚塗料組成物が組成物(B-2)を含む場合、防汚塗料組成物中の有機溶剤は、組成物(B-2)に由来する有機溶剤のみであってもよく、組成物(B-1)に由来する有機溶剤と由来しない有機溶剤(防汚塗料組成物の製造時に配合されたもの)との混合物であってもよい。
本発明の防汚塗料組成物は、共重合体(A-1)、共重合体(A-2)、有機溶剤及び防汚剤以外の他の成分をさらに含んでもよい。他の成分は、組成物(B)に由来するものであってもよく、由来しないもの(防汚塗料組成物の製造時に配合されたもの)であってもよく、それらの混合物であってもよい。
防汚剤としては、無機防汚剤、有機防汚剤等が挙げられ、要求性能に応じて1種または2種以上を適宜選択して使用することができる。
防汚剤としては、例えば、亜酸化銅、チオシアン銅、銅粉末等の銅系防汚剤、他の金属(鉛、亜鉛、ニッケル等)の化合物、ジフェニルアミン等のアミン誘導体、ニトリル化合物、ベンゾチアゾール系化合物、マレイミド系化合物、ピリジン系化合物等が挙げられる。これらは、1種を単独で、或いは2種以上を組み合わせて使用できる。
亜酸化銅と防汚剤(1)とを組み合わせる場合、配合比率(質量比)は、亜酸化銅/防汚剤(1)=80/20~99/1が好ましく、90/10~99/1がより好ましい。
亜酸化銅及び防汚剤(1)のいずれか一方または両方と、これら以外の他の防汚剤とを組み合わせてもよい。
他の成分としては、例えば共重合体(A-1)及び共重合体(A-2)以外の他の重合体が挙げられる。
他の重合体としては、例えば共重合体(A-1)及び共重合体(A-2)以外の熱可塑性樹脂(熱可塑性重合体)等が挙げられる。
本態様の防汚塗料組成物は、共重合体(A-1)及び共重合体(A-2)以外の熱可塑性樹脂を含むことが好ましい。防汚塗料組成物が前記熱可塑性樹脂を含むと、耐クラック性や耐水性等の塗膜物性が向上する。
可塑剤として機能し、塗膜の耐クラック性や耐剥離性の向上効果が得られる点では、塩素化パラフィンが好ましい。
沈降防止剤やたれ防止剤として機能し、防汚塗料組成物の貯蔵安定性や顔料分散性の向上効果が得られる点では、半合成ワックス、合成ワックス等の有機系ワックスが好ましく、ポリエチレンワックス、酸化ポリエチレンワックス、ポリアマイドワックスがより好ましい。
顔料としては、酸化亜鉛、タルク、シリカ、硫酸バリウム、カリ長石、水酸化アルミニウム、炭酸マグネシウム、マイカ、カーボンブラック、弁柄、酸化チタン、フタロシアニンブルー、カオリン、石膏等が挙げられる。特に、酸化亜鉛やタルクが好ましい。
熱可塑性樹脂以外の沈降防止剤やたれ防止剤としては、ベントナイト系、微粉シリカ系、ステアレート塩、レシチン塩、アルキルスルホン酸塩等が挙げられる。
防汚塗料組成物の水分含有量は、15質量%以下が好ましく、10質量%以下がより好ましい。下限は特に限定されず、0質量%であってもよい。水分含有量は、防汚塗料組成物の総質量に対する水の割合である。水分含有量が前記上限値以下であれば、防汚塗料組成物から形成される塗膜の耐水性、乾燥性がより優れる。
本発明の防汚塗料組成物のVOC含有量は、500g/L以下が好ましく、420g/L以下がより好ましく、400g/L以下がさらに好ましく、380g/L以下が特に好ましい。
VOC含有量は、防汚塗料組成物の比重及び固形分の値を用いて、下記式から算出される。
VOC含有量(g/L)=組成物の比重×1000×(100-固形分)/100
防汚塗料組成物の比重及び固形分はそれぞれ、後述する実施例に記載の方法により測定される。
VOC含有量は、有機溶剤の含有量により調整できる。
防汚塗料組成物の加熱残分は、70~100質量%が好ましく、70~90質量%がより好ましく、75~80質量%がさらに好ましい。防汚塗料組成物の加熱残分が前記範囲の下限値以上であれば、VOC含有量が充分に低くなる。加熱残分が前記範囲の上限値以下であれば、防汚塗料組成物の粘度を低くしやすい。
加熱残分は、後述する実施例に示す測定方法により測定される。
本発明の防汚塗料組成物の25℃における粘度は、5,000mPa・s未満であることが好ましく、4,000mPa・s未満がより好ましく、3,000mPa・s未満がさらに好ましく、2,000mPa・s未満が特に好ましい。防汚塗料組成物の粘度が前記上限値以下であれば、塗装しやすい。
防汚塗料組成物の25℃における粘度の下限は特に限定されないが、塗装時の塗料タレ抑制の点では、100mPa・s以上が好ましく、200mPa・s以上がより好ましく、300mPa・s以上がさらに好ましく、1,000mPa・s以上が特に好ましい。
したがって、防汚塗料組成物の25℃における粘度は、100mPa・s以上5,000mPa・s未満であることが好ましく、200mPa・s以上4,000mPa・s未満がより好ましく、300mPa・s以上3,000mPa・s未満がさらに好ましく、500mPa・s以上2,000mPa・s未満が特に好ましい。
防汚塗料組成物の粘度は、組成物(B)の粘度、組成物(B)への有機溶剤の添加量等によって調整できる。
本態様の防汚塗料組成物を用いた塗膜は、基材表面に、直接に、または下地塗膜を介して形成することができる。
下地塗膜としては、ウオッシュプライマー、塩化ゴム系やエポキシ系等のプライマー、中塗り塗料等を用いて形成できる。
塗膜の形成は、公知の方法により行うことができる。例えば、基材表面又は基材上の下地塗膜の上に、防汚塗料組成物を、刷毛塗り、吹き付け塗り、ローラー塗り、沈漬塗り等の手段で塗布し、乾燥することにより塗膜を形成できる。
防汚塗料組成物の塗布量は、一般的には乾燥塗膜として10~400μmの厚さになる量に設定できる。
塗膜の乾燥は、通常、室温で行うことができ、必要に応じて加熱乾燥を行ってもよい。
本発明の第六の態様は、単量体(a1)、単量体(a2)及び単量体(a3)からなる群から選ばれる少なくとも1種の単量体(a)と、マクロモノマー(b)と、を含む単量体混合物を重合して(メタ)アクリル系共重合体を得る工程を含む、(メタ)アクリル系共重合体の製造方法である。前記単量体混合物は、単量体(c)をさらに含んでもよい。
本態様の製造方法で製造される(メタ)アクリル系共重合体としては、前記共重合体(A-1)又は前記共重合体(A-2)が好ましい。
重合は、公知の重合開始剤を用いて、公知の方法で行えばよい。例えば、上記した単量体混合物をラジカル重合開始剤の存在下に60~180℃(さらには60~120℃)の反応温度で4~14時間(さらには5~10時間)反応させる方法が挙げられる。重合の際、必要に応じて、連鎖移動剤を用いてもよい。
重合開始剤の含有量は、特に限定されず、適宜設定することができる。典型的には、重合性単量体100質量部に対して0.1~20質量部程度である。
連鎖移動剤の含有量は、特に限定されず、適宜設定することができる。典型的には、重合性単量体100質量部に対して0.0001~10質量部程度である。
本態様の(メタ)アクリル系共重合体の製造方法にあっては、単量体(a)とマクロモノマー(b)とを含む単量体混合物を重合するため、得られる(メタ)アクリル系共重合体は、第一の態様の共重合体(A-1)や第二の態様の重合体溶液と同様の効果を奏し得る。例えばこの(メタ)アクリル系共重合体を用いた塗膜の硬度及び耐水性が優れる。この塗膜は、海水中等における静置防汚性にも優れ、また、優れた防汚効果が長期にわたって安定的に発揮される。
共重合体(A-1)や共重合体(A-2)の製造に本態様の製造方法を用いることで、形成される塗膜の硬度及び耐水性をより優れたものとすることができる。
前述の特許文献2では、マクロモノマーとカルボキシ基含有エチレン性不飽和単量体とを含み、2価金属含有エチレン性不飽和単量体を含まない単量体混合物を重合し、そこに2価金属含有エチレン性不飽和単量体を含む単量体混合物を滴下して重合し、ビニル系ポリマーを得て、その後、水を加えてビニル系ポリマーが水に分散した水性防汚塗料用樹脂組成物を得ている。この方法で得た水性防汚塗料用樹脂組成物を用いた塗膜は、耐水性に劣る。これは、マクロモノマーと2価金属含有エチレン性不飽和単量体とが異なる単量体混合物に配合されていること、水分散体とするためにアミンが含まれていること等が影響していると考えられる。また、1日後の塗膜の硬度も劣る。これは、水系のため、乾燥性が低いためと考えられる。
実施例中の評価は、以下に示す方法で行った。
測定試料(重合体溶液、重合体含有組成物、防汚塗料組成物等)0.50gをアルミニウム製の皿に測りとり、トルエン3mLをスポイトで加えて皿の底に一様に広げ、予備乾燥を行った。予備乾燥は、測定試料を皿全体にのばし、本乾燥で有機溶剤を揮発させやすくするための処理である。予備乾燥では、70~80℃の水浴上で測定試料及びトルエンを加熱溶解させ、蒸発乾固させた。予備乾燥後、105℃の熱風乾燥機で2時間の本乾燥を行った。測定試料の予備乾燥前の質量(乾燥前質量)と、本乾燥後の質量(乾燥後質量)とから、以下の式により加熱残分を求め、その値を固形分とした。
加熱残分(質量%)=乾燥後質量/乾燥前質量×100
乾燥したガードナー気泡粘度管(以下、単に粘度管ともいう。)に測定試料を粘度管の指示線まで入れコルク栓で栓をした。測定試料を採取した粘度管を、規定の温度(25.0±0.1℃)に調節した恒温水槽中に少なくとも2時間垂直に浸漬して測定試料を恒温にし、基準管となる粘度管と測定試料を入れた粘度管を同時に180°回転させ、測定試料のアワ上昇速度を基準管と比較することで、粘度(ガードナー粘度)を決定した。
測定試料の粘度を25℃においてB型粘度計で測定し、その値をB型粘度として示した。
・構成単位(A-3)を含むメタ(アクリル)系共重合体:
ゲル透過クロマトグラフィー(GPC)(東ソー株式会社製HLC-8220)を用いて測定した。メタ(アクリル)系共重合体を0.4質量%になるようにN,N-ジメチルホルムアミド(DMF)溶液を調製し、東ソー社製カラム(TSKgelα-M(東ソー株式会社製、7.8mm×30cm)、TSKguardcolumnα(東ソー株式会社製、6.0mm×4cm))が装着された装置に、上記の溶液を100μl注入して、40℃で測定を行った。標準ポリスチレン換算にて重量平均分子量(Mw)または数平均分子量(Mn)を算出した。
・構成単位(A1)及び(A2)からなる群から選ばれる少なくとも1種の構成単位を含むメタ(アクリル)系共重合体、マクロモノマー(b):
ゲル透過クロマトグラフィー(GPC)(東ソー株式会社製HLC-8320)を用いて測定した。共重合体及びマクロモノマーを0.2質量%になるようにテトラヒドロフラン溶液を調整し、東ソー社製カラム(TSKgel SuperHZM-M×HZM-M×HZ2000、TSKguardcolumn SuperHZ-L)が装着された装置に上記の溶液10μlを注入し、流量:0.35ml/分、溶離液:テトラヒドロフラン(安定剤BHT)、カラム温度:40℃の条件で測定し、標準ポリスチレン換算にて重量平均分子量(Mw)または数平均分子量(Mn)を算出した。
測定試料約0.5gをビーカーに精秤し(A(g))、トルエン/エタノール溶液50mLを加えた。フェノールフタレイン数滴を加え、0.5規定のKOH溶液にて滴定した。(滴定量=B(mL)、KOH溶液の力価=f)。ブランク測定を同様に行い(滴定量=C(mL))、以下の式に従って算出した。
酸価(mgKOH/g)={(B-C)×0.2×56.11×f}/A/固形分
測定試料のVOC含有量は、下記式により算出した。
VOC含有量(g/L)=測定試料の比重×1000×(100-固形分)/100
測定試料の比重は、25℃において、容量が100mLの比重カップに測定試料を満たし、質量を測定することにより算出した。
ガラス基板上に、重合体含有組成物を500μmアプリケーターで塗布して、25℃で1週間乾燥して塗膜を形成し、試験板を得た。この試験板の塗膜について、超微小硬度計(株式会社フィッシャー・インストルメンツ製試料、商品名:HM2000)によりマルテンス硬度(HM)を測定した。測定条件は、dQRST(F)/dt=一定、F(試験力)=10mN/10秒、C(最大荷重クリープ時間)=5秒、最大押し込み荷重10mN、最大押し込み深さ6μmとした。同じ塗膜のそれぞれ異なる3箇所についてマルテンス硬度を測定し、それらの平均値を塗膜の硬度とした。
なお、マルテンス硬度(HM)は1.2~15.0N/mm2の範囲であることが好ましく、2.0~10.0N/mm2の範囲であることがより好ましい。
上記塗膜硬度を測定するのと同様にし、ただし、乾燥時間を25℃で1日とした。
塗装後の塗膜の平滑性を目視で確認し、以下の基準で塗装適性を評価した。
○:塗膜が平滑。
△:塗膜にややムラがある。
×:塗膜にスジが残る。
ガラス基板上に、試料(重合体含有組成物)を500μmアプリケーターで塗布して、室温で1週間乾燥して塗膜を形成し、試験板を得た。この試験板を滅菌濾過海水中に1ヶ月間浸漬した後、この試験板を温度20℃の室温で1週間乾燥させた。白化度について、該試験板の塗膜表面を目視で観察した。評価は以下の基準で行った。
○:白化が観察されない。
△:少し白化が観察される。
×:かなり白化が観察される。
ガラス基板上に、試料(重合体含有組成物又は防汚塗料組成物)を500μmアプリケーターで塗布して、室温で1週間乾燥して塗膜を形成し、試験板を得た。この試験板を滅菌濾過海水中に1ヶ月間浸漬した後、この試験板を温度20℃の室温で1週間乾燥させた。乾燥後の試験板のヘイズをヘイズメータ(村上色彩技術研究所製、商品名:HM-150)で測定した。ヘイズ値が小さいほど、塗膜表面の白化度が低く、耐水性に優れることを示す。
防汚塗料組成物を、50mm×50mm×2mm(厚さ)の硬質塩化ビニル板に、乾燥膜厚120μmになるようにアプリケーターで塗布し、乾燥して塗膜を形成し、試験板を得た。この試験板を、海水中に設置した回転ドラムに取り付け、周速7.7m/s(15ノット)で回転させて3カ月後の塗膜の膜厚を測定した。測定された膜厚から、1ヶ月当りの消耗膜厚((120μm-測定された膜厚(μm))/3)を算出し、その値を消耗度とした。消耗度は、1~30μ/Mが好ましい。
防汚塗料組成物を、150mm×70mm×1.6mm(厚さ)のあらかじめ防錆塗料を塗布してあるサンドブラスト鋼板に、乾燥膜厚が120μmになるようにはけで塗布し、乾燥して塗膜を形成し、試験板を得た。この試験板を海中に浸漬し、3ヶ月間静置した後、塗膜の全面積に対する海中生物が付着した面積の割合(海中生物の付着面積)(%)を求め、海洋生物の付着面積が30%以下である場合を静置防汚性が良好とした。
単量体(a1-1):1-ブトキシエチルメタクリレート(後述する製造例a1-1で合成した合成品)。
単量体(a1-2):1-イソブトキシエチルメタクリレート(後述する製造例a1-2で合成した合成品)。
単量体(a1-3):1-(2-エチルへキシルオキシ)エチルメタクリレート(後述する製造例a1-3で合成した合成品)。
単量体(a2-1):トリイソプロピルシリルアクリレート(TIPX)。
単量体(a3-1):金属含有単量体混合物(後述する製造例a3-1で合成した合成品)。
単量体(a3-2):金属含有単量体混合物(後述する製造例a3-2で合成した合成品)。
マクロモノマー(MM2):後述する製造例MM2で得た数平均分子量2500のマクロモノマー。
マクロモノマー(MM3):後述する製造例MM3で得た数平均分子量3600のマクロモノマー。
マクロモノマー(MM4):後述する製造例MM4で得た数平均分子量6700のマクロモノマー。
MA:メチルアクリレート。
EA:エチルアクリレート。
BA:n-ブチルアクリレート。
MTMA:2-メトキシエチルメタクリレート。
MTA:2-メトキシエチルアクリレート。
MAA: メタクリル酸。
AIBN:2,2’-アゾビスイソブチロニトリル。
AMBN:2,2’-アゾビス(2-メチルブチロニトリル)。
ノフマーMSD:商品名、日油株式会社製、α-メチルスチレンダイマー。
添加剤(1):トヨパラックス(登録商標)150(東ソー(株)製、塩素化パラフィン)。
添加剤(2):ディスパロン(登録商標)4200-20(楠本化成(株)製、酸化ポリエチレンワックス)。
添加剤(3):ディスパロンA603-20X(楠本化成(株)製、ポリアマイドワックス)。
添加剤(4):KF-56(信越化学工業(株)製、シリコーンオイル)。
ブチルビニルエーテル150.2部(1.5mol)、ヒドロキノン0.24部、フェノチアジン0.47部を室温で撹拌して均一になるまで混合した。空気(10mL/min)を吹込みながら、メタクリル酸86.1部(1.0mol)、反応液の温度が60℃以下を保つようにして滴下した。滴下後、反応液の温度を80℃まで上げて、5時間反応させた。反応液にt-ブチルメチルエーテル264.5部(3.0mol)を加えて混合し、有機相を20質量%炭酸カリウム(水溶液350部で1回洗浄した。有機相に4-ベンゾイルオキシ-2,2,6,6-テトラメチルピペリジン-N-オキシル0.06部を加え、エバポレータにより低沸分を留出させた。得られた残渣を減圧蒸留して、沸点70℃/5torr(667Pa)の1-ブトキシエチルメタクリレート(単量体(a1-1))166.9部(0.91mol)を得た。
イソブチルビニルエーテル90.1部(0.9mol)、ヒドロキノン0.14部、フェノチアジン0.28部を室温で撹拌して均一になるまで混合した。空気(10ml/min)を吹込みながら、メタクリル酸51.7部(0.6mol)を、反応液の温度が60℃以下を保つようにして滴下した。滴下後、反応液の温度を80℃まで上げて、6時間反応させた。反応液にt-ブチルメチルエーテル158.7部(1.8mol)を加えて混合し、有機相を20質量%炭酸カリウム水溶液200部で1回洗浄した。有機相に4-ベンゾイルオキシ-2,2,6,6-テトラメチルピペリジン-N-オキシル0.03部を加え、エバポレータにより低沸分を留出させた。得られた残渣を減圧蒸留して、沸点60℃/3torrの1-イソブトキシエチルメタクリレート(単量体(a1-2))97.5部(0.52mol)を得た。
2-エチルへキシルビニルエーテル171.9部(1.1mol)、ヒドロキノン0.32部、フェノチアジン0.61部を室温で撹拌して均一になるまで混合した。空気(10ml/min)を吹込みながら、メタクリル酸86.1部(1.0mol)を、反応液の温度が60℃以下を保つようにして滴下した。滴下後、反応液の温度を80℃まで上げて、
5時間反応させた。反応液にt-ブチルメチルエーテル264.5部(3.0mol)を加えて混合し、有機相を20質量%炭酸カリウム水溶液135部で1回洗浄した。有機相に4-ベンゾイルオキシ-2,2,6,6-テトラメチルピペリジン-N-オキシル0.07部を加え、エバポレータにより低沸分を留出させた。得られた残渣を減圧蒸留して、沸点99℃/3torrの1-(2-エチルへキシルオキシ)エチルメタクリレート(単量体(a1-3))207.0部(0.85mol)得た。
冷却器、温度計、滴下ロート及び攪拌機を備えた四つ口フラスコにプロピレングリコールメチルエーテル(PGM)85.4部及び酸化亜鉛40.7部を仕込み、撹拌しながら75℃に昇温した。続いて、滴下ロートからメタクリル酸43.1部、アクリル酸36.1部、水5部からなる混合物を3時間かけて一定速度で滴下した。滴下終了後反応溶液は乳白色状態から透明となった。さらに2時間撹拌した後n-ブタノールを36部添加して金属含有単量体混合物(単量体(a3-1))を得た。固形分は44.8質量%であった。
冷却器、温度計、滴下ロート及び攪拌機を備えた四つ口フラスコにプロピレングリコールメチルエーテル(PGM)100部及び酸化亜鉛40.7部を仕込み、撹拌しながら75℃に昇温した。続いて、滴下ロートからメタクリル酸30.1部、アクリル酸25.2部、オクチル酸43.3部からなる混合物を3時間かけて一定速度で滴下した。滴下終了後反応溶液は乳白色状態から透明となった。さらに2時間撹拌した後プロピレングリコールメチルエーテル(PGM)を21.3部添加して金属含有単量体混合物(単量体(a3-2))を得た。固形分は55.0質量%であった。
(分散剤1の製造)
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水900部、メタクリル酸2-スルホエチルナトリウム60部、メタクリル酸カリウム10部及びメチルメタクリレート(MMA)12部を入れて撹拌し、重合装置内を窒素置換しながら、50℃に昇温した。その中に、重合開始剤として2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩0.08部を添加し、更に60℃に昇温した。昇温後、滴下ポンプを使用して、MMAを0.24部/分の速度で75分間連続的に滴下した。反応溶液を60℃で6時間保持した後、室温に冷却して、透明な水溶液である固形分10質量%の分散剤1を得た。
撹拌装置を備えた合成装置中に、窒素雰囲気下で、酢酸コバルト(II)四水和物1.00g及びジフェニルグリオキシム1.93g、あらかじめ窒素バブリングにより脱酸素したジエチルエーテル80mlを入れ、室温で30分間攪拌した。ついで、三フッ化ホウ素ジエチルエーテル錯体10mlを加え、さらに6時間攪拌した。混合物をろ過し、固体をジエチルエーテルで洗浄し、15時間真空乾燥して、赤褐色固体である連鎖移動剤1を2.12g得た。
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水145部、硫酸ナトリウム0.1部及び分散剤1(固形分10質量%)0.25部を入れて撹拌し、均一な水溶液とした。次に、MMAを100部、連鎖移動剤1を0.008部及び1,1,3,3-テトラメチルブチルパーオキシ2-エチルヘキサノエート(パーオクタO(登録商標)、日油株式会社製)0.8部を加え、水性懸濁液とした。
次に、重合装置内を窒素置換し、80℃に昇温して1時間反応し、さらに重合率を上げるため、90℃に昇温して1時間保持した。その後、反応液を40℃に冷却して、ポリマーを含む水性懸濁液を得た。この水性懸濁液を目開き45μmのナイロン製濾過布で濾過し、濾過物を脱イオン水で洗浄し、脱水し、40℃で16時間乾燥することにより、マクロモノマー(MM1)を得た。マクロモノマー(MM1)の数平均分子量は1600であった。
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水145部、硫酸ナトリウム0.1部及び分散剤1(固形分10質量%)0.25部を入れて撹拌し、均一な水溶液とした。次に、MMAを100部、連鎖移動剤1を0.004部及び1,1,3,3-テトラメチルブチルパーオキシ2-エチルヘキサノエート(パーオクタO(登録商標)、日油株式会社製)0.4部を加え、水性懸濁液とした。
次に、重合装置内を窒素置換し、80℃に昇温して1時間反応し、さらに重合率を上げるため、90℃に昇温して1時間保持した。その後、反応液を40℃に冷却して、ポリマーを含む水性懸濁液を得た。この水性懸濁液を目開き45μmのナイロン製濾過布で濾過し、濾過物を脱イオン水で洗浄し、脱水し、40℃で16時間乾燥することにより、マクロモノマー(MM2)を得た。マクロモノマー(MM2)の数平均分子量は2500であった。
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水145部、硫酸ナトリウム0.1部及び分散剤1(固形分10質量%)0.25部を入れて撹拌し、均一な水溶液とした。次に、MMAを100部、連鎖移動剤1を0.003部及び1,1,3,3-テトラメチルブチルパーオキシ2-エチルヘキサノエート(パーオクタO、日油株式会社製)0.3部を加え、水性懸濁液とした。
次に、重合装置内を窒素置換し、80℃に昇温して1時間反応し、さらに重合率を上げるため、90℃に昇温して1時間保持した。その後、反応液を40℃に冷却して、ポリマーを含む水性懸濁液を得た。この水性懸濁液を目開き45μmのナイロン製濾過布で濾過し、濾過物を脱イオン水で洗浄し、脱水し、40℃で16時間乾燥することにより、マクロモノマー(MM3)を得た。マクロモノマー(MM3)の数平均分子量は3600であった。
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水145部、硫酸ナトリウム0.1部及び分散剤1(固形分10質量%)0.25部を入れて撹拌し、均一な水溶液とした。次に、MMAを100部、連鎖移動剤1を0.0015部及び1,1,3,3-テトラメチルブチルパーオキシ2-エチルヘキサノエート(パーオクタO、日油株式会社製)0.15部を加え、水性懸濁液とした。
次に、重合装置内を窒素置換し、80℃に昇温して1時間反応し、さらに重合率を上げるため、90℃に昇温して1時間保持した。その後、反応液を40℃に冷却して、ポリマーを含む水性懸濁液を得た。この水性懸濁液を目開き45μmのナイロン製濾過布で濾過し、濾過物を脱イオン水で洗浄し、脱水し、40℃で16時間乾燥することにより、マクロモノマー(MM4)を得た。マクロモノマー(MM4)の数平均分子量は6700であった。
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水145部、硫酸ナトリウム0.1部及び分散剤1(固形分10質量%)0.25部を入れて撹拌し、均一な水溶液とした。次に、MMAを75部、MTMA25部、連鎖移動剤1を0.01部及び1,1,3,3-テトラメチルブチルパーオキシ2-エチルヘキサノエート(パーオクタO、日油株式会社製)1.5部を加え、水性懸濁液とした。
次に、重合装置内を窒素置換し、80℃に昇温して1時間反応し、さらに重合率を上げるため、90℃に昇温して1時間保持した。その後、反応液を40℃に冷却して、ポリマーを含む水性懸濁液を得た。この水性懸濁液を目開き45μmのナイロン製濾過布で濾過し、濾過物を脱イオン水で洗浄し、脱水し、40℃で16時間乾燥することにより、マクロモノマー(MM5)を得た。マクロモノマー(MM5)の数平均分子量は2000であった。
撹拌機、温度調整機、滴下ロートを備えた反応容器に、キシレン48.3部を仕込み、窒素雰囲気下で、撹拌しながら85℃に昇温した。続いて、滴下ロートから単量体(a1-1)25部、マクロモノマー(MM1)10部、MMA7.5部、EA20部、MTMA37.5部、AIBN1.5部からなる混合物を4時間かけて等速滴下した。滴下終了30分後、t-ブチルパーオキシ2-エチルヘキサノエート2.0部とキシレン9部を30分間隔で4回滴下し、さらに1時間撹拌した後、ブチルビニルエーテル6.7部、酢酸ブチル2部を添加し、固形分59.7質量%、ガードナー粘度TUの溶液状の重合体含有組成物(重合体溶液)A-1を得た。
単量体及び開始剤のAIBNの仕込み量(部)を表1に示すようにしたこと以外は実施例1と同様にして、溶液状の重合体含有組成物A-2~A-11を製造した。
マクロモノマーを用いなかった比較例1~2の重合体含有組成物A-6、A-11は、固形分が同じレベルであるが、実施例1~9に比べて粘度が高かった。また、形成された塗膜の硬度が低く、耐水性も劣っていた。
表2に示す組成に従い、各成分を金属缶に仕込んだ後、ガラスビーズ70gを添加し、撹拌棒にてあらかじめ混合したものを、ロッキングシェーカーにより顔料分散することで、防汚塗料組成物を得た。
得られた防汚塗料組成物の評価結果を表2に示す。
マクロモノマーに基づく構成単位を含まない共重合体を用いた比較例3の防汚塗料組成物は、重合体含有組成物以外は同じ組成の実施例10~14に比べて、加熱残分、VOCが同じレベルであるが、塗料粘度が高く、塗装適性に劣っていた。比較例4と実施例18~20との対比においても同様の傾向が見られた。
実施例10、比較例3の防汚塗料組成物について静置防汚性を評価したところ、結果はそれぞれ良好であった。
撹拌機、温度調整機、滴下ロートを備えた反応容器に、キシレン40部、マクロモノマー(MM2)10部を仕込み、撹拌しながら90℃に昇温した。続いて、窒素雰囲気下で、滴下ロートからTIPX50部、MMA25部、EA10部、MTA5部、AMBN1.0部からなる混合物を4時間かけて等速滴下した。滴下終了30分後に、t-ブチルパーオキシ2-エチルヘキサノエート1.0部とキシレン10部を1時間半で滴下し、さらに1時間撹拌した後、固形分61.1質量%、B型粘度760mPa・sの溶液状の重合体含有組成物(重合体溶液)A-12を得た。
単量体及び開始剤のAIBNの仕込み量(部)を表1に示すようにしたこと以外は実施例21と同様にして、溶液状の重合体含有組成物A-13~A-14、A-16を製造した。
撹拌機、温度調整機、滴下ロートを備えた反応容器に、キシレン40部を仕込み、撹拌しながら90℃に昇温した。続いて、窒素雰囲気下で、滴下ロートからTIPX50部、マクロモノマー(MM2)10部、MMA25部、EA10部、MTA5部、AMBN1.0部からなる混合物を4時間かけて等速滴下した。滴下終了30分後に、t-ブチルパーオキシ2-エチルヘキサノエート1.0部とキシレン26部を1時間半で滴下し、さらに1時間撹拌した後、固形分61.1質量%、B型粘度690mPa・sの溶液状の重合体含有組成物(重合体溶液)A-15を得た。
マクロモノマーを用いなかった比較例5の重合体含有組成物A-16は、実施例21~24に比べて、固形分が同じレベルであるが粘度が高かった。また、塗膜硬度、塗装1日後の塗膜硬度が低かった。塗膜の耐水性は、良好ではあるものの、実施例21~24に比べて劣っていた。
表4に示す組成に従い、各成分を金属缶に仕込んだ後、ガラスビーズ70gを添加し、撹拌棒にてあらかじめ混合したものを、ロッキングシェーカーにより顔料分散することで、防汚塗料組成物を得た。
得られた防汚塗料組成物の評価結果を表4に示す。
比較例6の防汚塗料組成物の塗膜は、充分な消耗度を有していたが、比較例5の結果から、塗膜硬度、1日後の塗膜硬度及び耐水性が実施例25~28に比べて劣ると判断できる。
実施例25~28、比較例6の防汚塗料組成物について静置防汚性を評価したところ、結果はそれぞれ良好であった。
冷却器、温度計、滴下ロート及び攪拌機を備えた四つ口フラスコにPGM(プロピレングリコールメチルエーテル)15部、キシレン30部及びEA4.0部を仕込み、撹拌しながら100℃に昇温した。続いて、滴下ロートからMMAメチルメタクリレート23.0部、EA10部、BA30部、製造例a3-1で得た単量体(a3-1)28.8部(有機溶剤を含めた全量)、製造例MM1で得たマクロモノマー(MM1)20部、連鎖移動剤(日油株式会社製、ノフマー(登録商標)MSD)1.5部、AMBN13.0部からなる混合物を6時間かけて一定速度で滴下した。滴下終了後にt-ブチルパーオクトエート0.5部とキシレン8部を30分で滴下し、さらに1時間30分撹拌し、固形分57.2質量%、B型粘度390mPa・sの溶液状の重合体含有組成物(重合体溶液)A-17を得た。
単量体の仕込み量を表5~6に示すようにしたこと以外は実施例29と同様にして、溶液状の重合体含有組成物(重合体溶液)A-18~A-22、A-30~A-33、A-35~36を製造した。
なお、表5~6の単量体(a3)の配合量は、固形分量のみを記載している。
冷却器、温度計、滴下タンク及び攪拌機を備えた加圧重合可能なオートクレーブにPGM(プロピレングリコールメチルエーテル)15部及びキシレン30部及びEA4部を仕込み、撹拌しながら350kPaに加圧し145℃に昇温した。続いて、滴下タンクからMMA35部、EA5部、BA30部、製造例a3-1で得た単量体(a3-1)28.8部(有機溶剤を含めた全量)、連鎖移動剤(日本油脂社製ノフマーMSD)1.5部、AMBN6部からなる透明な混合物を4時間で等速滴下した。滴下終了後にt-ブチルパーオクトエート0.5部とキシレン7部を30分で滴下し、さらに1時間30分撹拌した後キシレンを8部添加して、300メッシュでろ過して溶液状の重合体含有組成物(重合体溶液)A-23を得た。
単量体の仕込み量を表5~6に示すようにしたこと以外は実施例35と同様にして、溶液状の重合体含有組成物(重合体溶液)A-24~A-29、A-37を製造した。
なお、表5~6の単量体(a3)の配合量は、固形分量のみを記載している。
撹拌機、温度調整機、滴下装置を備えた反応容器に、キシレン15部を仕込み、撹拌しながら130℃に昇温した。その後、下記原料からなる混合物を、2時間かけて等速滴下し、更に0.5時間共重合反応を行った。
マクロモノマー(MM1):20部、
BA:20部、
MAA:7部、
AMBN:3部。
単量体(a3-1):28.8部、
MMA:16部、
EA:9部、
BA:10部、
ノフマーMSD(日油株式会社製):1.5部、
AMBN:10部。
マクロモノマーを用いなかった比較例7の樹脂組成物の塗膜は、硬度及び耐水性ともに劣っていた。また、重合体含有組成物の粘度が高かった。
25℃におけるB型粘度が5×104mPa・s超の重合体溶液を水に分散させた水性分散液であり、有機溶剤の含有量が、共重合体を除いた全量に対して30質量%未満である比較例8の重合体含有組成物の塗膜は、1日後の塗膜硬度が低く、耐水性に劣っていた。また、重合体溶液が高粘度であり、ハンドリング性が低かった。
表7~8に示す組成に従い、各成分を高速ディスパーにより混合して、防汚塗料組成物を得た。得られた防汚塗料組成物を用いて形成された塗膜の性能(消耗度)の評価結果を表7~8に示す。
比較例9の防汚塗料組成物の塗膜は、充分な消耗度を有していたが、比較例7の結果から、塗膜硬度、1日後の塗膜硬度及び耐水性が低いと判断できる。
比較例10の防汚塗料組成物の塗膜は、実施例48~68に比べて消耗度が少なかった。そのため、防汚性に劣ると判断できる。また、比較例8の結果から、耐水性が低いと判断できる。
実施例48、51、比較例9の防汚塗料組成物について静置防汚性を評価したところ、結果はそれぞれ良好であった。
Claims (16)
- 下記式(1)、下記式(2)又は下記式(3)で表される構造からなる群から選ばれる少なくとも1種の構造(I)を有する構成単位(A1)、及びトリオルガノシリルオキシカルボニル基を有する構成単位(A2)からなる群から選ばれる少なくとも1種の構成単位と、マクロモノマー(b)由来の構成単位(B)と、を有する(メタ)アクリル系共重合体。
- 下記式(4)又は(5)で表される構造からなる群から選ばれる少なくとも1種の構造(III)を有する構成単位(A3)と、マクロモノマー(b)由来の構成単位(B)と、を有する(メタ)アクリル系共重合体と、
有機溶剤と、を含み、
25℃における粘度が、5×104mPa・s以下である、重合体溶液。
-COO-M-OCO ・・・(4)
-COO-M-R32 ・・・(5)
(式中、MはZn、Cu、Mg又はCaを示し、R32は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。) - 請求項2に記載の重合体溶液を含み、有機溶剤の含有量が、前記(メタ)アクリル系共重合体を除いた全量に対して30質量%以上である、重合体含有組成物。
- 水分含有量が15質量%以下である、請求項3に記載の重合体含有組成物。
- 前記マクロモノマー(b)が、下記式(b’)で表される構成単位を2以上有する、数平均分子量が500~50000であるマクロモノマーである、請求項1に記載の(メタ)アクリル系共重合体。
- 前記マクロモノマー(b)が、下記式(b’)で表される構成単位を2以上有する、数平均分子量が500~50000であるマクロモノマーである、請求項2に記載の重合体溶液。
- 前記マクロモノマー(b)が、下記式(b’)で表される構成単位を2以上有する、数平均分子量が500~50000であるマクロモノマーである、請求項3又は4に記載の重合体含有組成物。
- 請求項1に記載の(メタ)アクリル系共重合体を含む、重合体含有組成物。
- 前記(メタ)アクリル系共重合体が前記構成単位(A1)を有し、
下記式(11)で表される化合物、下記式(12)で表される化合物、及び下記式(13)で表される化合物からなる群から選ばれる少なくとも1種のアルケニル化合物をさらに含む、請求項8に記載の重合体含有組成物。
- 請求項3、4、7~9のいずれか一項に記載の重合体含有組成物を含む、防汚塗料組成物。
- 防汚剤をさらに含む、請求項10に記載の防汚塗料組成物。
- 前記防汚剤が、亜酸化銅、4-ブロモ-2-(4-クロロフェニル)-5-(トリフルオロメチル)-1H-ピロール-3-カルボニトリル、トリフェニルボラン及びメデトミジンからなる群から選ばれる少なくとも1種を含む、請求項11に記載の防汚塗料組成物。
- 25℃における粘度が、5000mPa・s以下である、請求項10~12のいずれか一項に記載の防汚塗料組成物。
- VOC含有量が、500g/L以下である、請求項10~13のいずれか一項に記載の防汚塗料組成物。
- 前記(メタ)アクリル系共重合体以外の熱可塑性樹脂をさらに含む、請求項10~14のいずれか一項に記載の防汚塗料組成物。
- 下記式(1)、下記式(2)又は下記式(3)で表される構造からなる群から選ばれる少なくとも1種の構造(I)を有する単量体(a1)、トリオルガノシリルオキシカルボニル基を有する単量体(a2)、及び下記式(a3-1)で表される単量体及び下記式(a3-2)で表される単量体からなる群から選ばれる少なくとも1種の単量体(a3)からなる群から選ばれる少なくとも1種の単量体(a)と、
マクロモノマー(b)と、
を含む単量体混合物を重合して(メタ)アクリル系共重合体を得る工程を含む、(メタ)アクリル系共重合体の製造方法。
CH2=C(R31)-CO-O-M-R32 ・・・(a3-2)
(式中、Xは-O-、-S-又は-NR14-を示し、R14は水素原子又はアルキル基を示し、R1及びR2はそれぞれ、水素原子又は炭素数1~10のアルキル基を示し、R3及びR5はそれぞれ、炭素数1~20のアルキル基、シクロアルキル基又はアリール基を示し、R4及びR6はそれぞれ、炭素数1~10のアルキレン基を示し、MはZn、Cu、Mg又はCaを示し、R31は水素原子又はメチル基を示し、R32は(メタ)アクリロイルオキシ基以外の有機酸残基を示す。)
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US20200115480A1 (en) * | 2017-06-30 | 2020-04-16 | Fujifilm Corporation | Composition, optical film, polarizing plate, display device, and method for producing composition |
US11613596B2 (en) * | 2017-06-30 | 2023-03-28 | Fujifilm Corporation | Composition, optical film, polarizing plate, display device, and method for producing composition |
CN111479882A (zh) * | 2017-11-24 | 2020-07-31 | 佐敦有限公司 | 防污组合物 |
US11111406B2 (en) | 2018-07-03 | 2021-09-07 | Nippon Paint Marine Coatings Co., Ltd. | Copolymer and antifouling coating composition containing the same |
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WO2022210521A1 (ja) * | 2021-03-31 | 2022-10-06 | 三菱ケミカル株式会社 | 化合物、重合体及び防汚塗料組成物 |
WO2022210547A1 (ja) * | 2021-03-31 | 2022-10-06 | 三菱ケミカル株式会社 | 化合物、重合体及び防汚塗料組成物 |
KR20230161937A (ko) | 2021-03-31 | 2023-11-28 | 미쯔비시 케미컬 주식회사 | 화합물, 중합체 및 방오 도료 조성물 |
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SG10201911773YA (en) | 2020-02-27 |
KR102036317B1 (ko) | 2019-10-24 |
EP3872137A1 (en) | 2021-09-01 |
US20220144987A1 (en) | 2022-05-12 |
JP6369563B2 (ja) | 2018-08-08 |
JP2018197341A (ja) | 2018-12-13 |
JP7001116B2 (ja) | 2022-01-19 |
JP2020094222A (ja) | 2020-06-18 |
CN108137760B (zh) | 2022-03-15 |
EP3354667A1 (en) | 2018-08-01 |
CN108137760A (zh) | 2018-06-08 |
SG10201911771XA (en) | 2020-02-27 |
US11643489B2 (en) | 2023-05-09 |
TW201714902A (zh) | 2017-05-01 |
JP2020094221A (ja) | 2020-06-18 |
EP3584290A1 (en) | 2019-12-25 |
JP2018184610A (ja) | 2018-11-22 |
KR20190037369A (ko) | 2019-04-05 |
KR102073149B1 (ko) | 2020-02-04 |
US20180201797A1 (en) | 2018-07-19 |
JP7001117B2 (ja) | 2022-01-19 |
SG11201802099YA (en) | 2018-04-27 |
KR20180041732A (ko) | 2018-04-24 |
KR20190037368A (ko) | 2019-04-05 |
JPWO2017051922A1 (ja) | 2017-09-21 |
EP3354667B1 (en) | 2021-04-07 |
EP3354667A4 (en) | 2018-08-15 |
EP3584290B1 (en) | 2021-07-21 |
KR101991228B1 (ko) | 2019-09-30 |
EP3872137B1 (en) | 2022-10-26 |
TWI609892B (zh) | 2018-01-01 |
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