CA1091390A - Hydrophilic polymer - Google Patents
Hydrophilic polymerInfo
- Publication number
- CA1091390A CA1091390A CA254,537A CA254537A CA1091390A CA 1091390 A CA1091390 A CA 1091390A CA 254537 A CA254537 A CA 254537A CA 1091390 A CA1091390 A CA 1091390A
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- monomer
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- weight
- methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for the preparation of hydrophilic polymers comprising copolymerizing a monomer mixture comprising (a) 5 to 30% by weight of a carboxyl group-containing ethylenically unsaturated monomer, (b) 5 to 90% by weight of an amino group-containing ethylenically unsaturated monomer and (c) a balance of an another monomer copolymerizable with the aforesaid monomers.
A process for the preparation of hydrophilic polymers comprising copolymerizing a monomer mixture comprising (a) 5 to 30% by weight of a carboxyl group-containing ethylenically unsaturated monomer, (b) 5 to 90% by weight of an amino group-containing ethylenically unsaturated monomer and (c) a balance of an another monomer copolymerizable with the aforesaid monomers.
Description
109139() This invention relates to hydrophylic polymers and a process for preparation of the same. More particularly, it relates to novel hydrophilic copolymers which provide coating films firmly bonded to substrates and are suitably used as - 5 coating for underwater constructions, anti-fogging coating, hydrophilic layer in transfer paper, hydrophilic layer in planographic plate and the like, and a process for the pre-paration of the same.
; It is known that hydrophilic acrylate and metha-crylate polymers and copolymers, such as poly(2-hydroxyethyl acrylate), poly(2-hydroxyethyl methacrylate), 2-hydroxyethyl acrylate copolymers and 2-hydroxyethyl methacrylate copolymers, reduce hydraulic resistance, on account of their water absorb-ing capacities, when used as, e.g., ship bottom paint, as disclosed in Japanese Patent Specification layed open No.
14885/1972 and Japanese Patent Specification published for public inspection No. 8730/1975. It is also known that coat-, ing films including such a hydrophylic polymer or copolymer as mentioned above exhibit anti-fogging property, as disclosed 20 in United States Patent Nos. 3,515,579 and 3,635,756. However, such known hydrophilic polymers and copolymers are of low practical value because of poor adhesion to substrate and poor mechanical strength of coating films made thereof. The aforesaid acrylate and methacrylate polymers and copolymers are in general crosslinked by, e.g., ammonium bichromate when used as coating for underwater construction because they possess desirable properties for such uses, i.e. high :
water absorbing capacity and water insolubility, but provide coating films of a low mechanical strength as such. The crosslinking by means of ammonium bichromate requires light, and it can be completed within a short period of time by the irradiation of ultraviolet rays, though it requires in dark plaoe a .. ~k ~09139Q
reaction time of 3 to 7 days because of a very low reaction rate in the absence of light. Therefore, in this process, it is necessary for coated objects to be exposed to light or let be for a long period of time.
Other than the ammonium bichromate, there are many compounds capable of reacting with hydroxyl group to cross-link the aforesaid polymers and copolymers and, among them, isocyanate compounds readily react at room temperature, but they are of no value as crosslinking agent because solvents for poly(2-hydroxyethyl methacrylate) and like polymers usually employed are polar solvent and there occurs reaction between the isocyanate compound and the solvent. In the above Japanese Patent Specification layed open, there is disclosed a process for improving the low mechanical strength by copolymerizing the hydrophilic, hydroxyl group-containing ethylenically unsaturated monomer with another ethylenically unsaturated monomer, though the copolymerization afford copolymers of a decreased water absorbing capacity and have not good hydrophilic effect above mentioned.
, 20 Accordingly, an object of an aspect of the present invention is to provide a novel polymer which is water insoluble and water absorptive and forms a coating film of a high mechanical strength.
An object of an aspect of the present invention is to provide a process for the preparation of a water insoluble and water absorptive copolymer capable of forming a coating film of high mechanical strength.
An object of an aspect of the present invention is to provide a resinous composition capable of forming a water insoluble and water absorptive coating film of a high mechanical strength.
An object of an aspect of the present invention is to provide underwater constructions coated with a hydrophilic : polymer-of high mechanical strength.
. In accordance with one aspect of this invention there is provided a water-insoluble hydrophilic coating composition comprising (A) water-insoluble hydrophilic copolymer having a water absorbing capacity of 10 to 250% by weight comprising (a) 5 to 30% by weight of at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and citraconic acid, . (b) 5 to 90% by weight of at least one member selected from the group consisting of (i) amino group-containing ethyl-enically unsaturated monomer having the general formula I:
CH2=CRl 1OOR2N~ ( I ) wherein R4 , R2 is alkylene having 1 - 4 carbon atoms, and R3 and R4 are alkyl having 1 - 4 carbon atoms and (ii) diacetone acrylamide, (c) a balance of at least one ethylenically unsaturated ' monomer selected from the group consisting of . (i) a monomer having the general formula II:
; CH2=CR5 COOR6 (II) wherein R5 is H or CH3 and R6 is alkyl having 1 - 12 carbon atoms and (ii) a monomer having the general formula III: `-CH2=CR7 COO(R8O)H (III) ~ ¢~ ' 10~1390 ' wherein R7 is H or CH3 and . R8 is alkylene having 2 - 3 carbon atoms and (B) 5 to 20~ by weight, based on the weight of said copolymer, of a crosslinking agent.
In-the present invention, the above problems have been solved by means of a coating of a copolymer obtained by copolymerizing a monomer mixture containing 5 to 30, preferably 8 to 15% by weight of a carboxyl group-containing ethylenically unsaturated monomer, 5 to 90, preferably 10 to 80% by weight of an amino group-containing ethylenically unsaturated monomer and a balance of the total 100% by weight ;:
of another monomer capable of copolymerizing with the aforesaid monomers. While the mechanism of regulating the water 15 absorbing capacity of the resulting copolymer is uncertain, ~ -it is essential that both carboxyl groups and amino groups -~
- coexist with each other in a polymerization system and the coexistence of the both groups makes it possible to regulate the water absorbing capacity of coating freely within the range from 10% by weight to 250% by weight. It will be ~-: worthy of special mention that there may be employed as :~
solvent for the copolymer not only polar solvents but also :
non-polar solvents, such as toluene, xylene and like aromatics and ethyl acetate, butyl . .
- 4a -~09139~J
acetate and like esters. Thus~ in accordance with the pre-sent invention, as crosslinking agent there may be used isocyanates which are unusable in polar solvents. In addi-` tion, the amino groups contained in the polymeric system makes it easy to completely react with an epoxy compound atroom temperature. And, the resulting coating exhibits a good adhesion to substrates.
The hydrophilic copolymer in accordance with the present invention is useful as, e.g., coatings for underwater constructions and anti-fogging coatings.
The term "underwater construction" so far as used in this specification means watercraft and underwater static structures. The term "watercraft" means àll sorts of movable structures such as, e.g., sailboats, yachts, motor boats, canoes, water skis, surfboards, ocean liners, tugboats, tan-ker and warship. The term underwater static structures means quay wall, pier, bridge and other various at least partly submerged fixed structures. The surfaces of the underwater constructions may be formed of metals, wood, plastics, concrete and other solids. The coating in accordance with the present invention is of great value as ship coating which imparts to such movable or fixed structures resistance against fouling by barnacle, algae, slime, oyster, ascidian and like marine ~; living things.
As anti-fogging coating it may be applied to the surfaces of e.g., glasses, sunglasses, goggles, mirror, win-- dowpane and aluminum sash. A transfer paper may be prepared by forming a layer of the hydrophilic copolymer on a substrate and then applying thereover a layer of a water soluble paste and a layer of a dye paste. A planographic plate may be prepared by forming a layer of the hydrophilic copolymer on ~ - 5 -,.
~091390 an aluminum plate or like base material and applying there-over a photosensiti~e layer.
It is essential for the copolymer of the present invention that it is water insoluble and has a water absorb-ing capacity of 10 to 250, preferably 40 to 150~ by weight.
The polymer has an intrinsic viscosity of 0.05 to 3.0, preferably 0.08 to 2.0, most preferably 0.1 to 1.5 when a solution dissolved 1 g of the polymer into 25 ml of methyl-; cellosolve is measured by an Ostwald viscometer at a tempera-ture of 20C.
The carboxyl group-containing ethylenically unsatu~
rated monomer suitably used in the practice of the present ; invention includes, e.g., acrylic acid, metnacrylic acid, maleic anhydride, fumaric acid, itaconic acid and citraconic acid, and may be used in an amount of 5 to 30, preferably 8 to 15% by weight. In amounts less than 5% by weight, the coating film formed is insufficient in adhesion to substrate while, on the other hand, in amounts exceeding 30% by weight, the coating film becomes readily peelable when swollen.
The amino group-containing ethylenically unsaturated monomer includes, e.g., acrylamide, methacrylamide; N-methyl acrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopr acrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylmide, N-isopropylmeth-25 acrylamide, N-butylmethacrylamide and like N-alkylated acrylamides and methacrylamides; diacetoneacrylamide;
; It is known that hydrophilic acrylate and metha-crylate polymers and copolymers, such as poly(2-hydroxyethyl acrylate), poly(2-hydroxyethyl methacrylate), 2-hydroxyethyl acrylate copolymers and 2-hydroxyethyl methacrylate copolymers, reduce hydraulic resistance, on account of their water absorb-ing capacities, when used as, e.g., ship bottom paint, as disclosed in Japanese Patent Specification layed open No.
14885/1972 and Japanese Patent Specification published for public inspection No. 8730/1975. It is also known that coat-, ing films including such a hydrophylic polymer or copolymer as mentioned above exhibit anti-fogging property, as disclosed 20 in United States Patent Nos. 3,515,579 and 3,635,756. However, such known hydrophilic polymers and copolymers are of low practical value because of poor adhesion to substrate and poor mechanical strength of coating films made thereof. The aforesaid acrylate and methacrylate polymers and copolymers are in general crosslinked by, e.g., ammonium bichromate when used as coating for underwater construction because they possess desirable properties for such uses, i.e. high :
water absorbing capacity and water insolubility, but provide coating films of a low mechanical strength as such. The crosslinking by means of ammonium bichromate requires light, and it can be completed within a short period of time by the irradiation of ultraviolet rays, though it requires in dark plaoe a .. ~k ~09139Q
reaction time of 3 to 7 days because of a very low reaction rate in the absence of light. Therefore, in this process, it is necessary for coated objects to be exposed to light or let be for a long period of time.
Other than the ammonium bichromate, there are many compounds capable of reacting with hydroxyl group to cross-link the aforesaid polymers and copolymers and, among them, isocyanate compounds readily react at room temperature, but they are of no value as crosslinking agent because solvents for poly(2-hydroxyethyl methacrylate) and like polymers usually employed are polar solvent and there occurs reaction between the isocyanate compound and the solvent. In the above Japanese Patent Specification layed open, there is disclosed a process for improving the low mechanical strength by copolymerizing the hydrophilic, hydroxyl group-containing ethylenically unsaturated monomer with another ethylenically unsaturated monomer, though the copolymerization afford copolymers of a decreased water absorbing capacity and have not good hydrophilic effect above mentioned.
, 20 Accordingly, an object of an aspect of the present invention is to provide a novel polymer which is water insoluble and water absorptive and forms a coating film of a high mechanical strength.
An object of an aspect of the present invention is to provide a process for the preparation of a water insoluble and water absorptive copolymer capable of forming a coating film of high mechanical strength.
An object of an aspect of the present invention is to provide a resinous composition capable of forming a water insoluble and water absorptive coating film of a high mechanical strength.
An object of an aspect of the present invention is to provide underwater constructions coated with a hydrophilic : polymer-of high mechanical strength.
. In accordance with one aspect of this invention there is provided a water-insoluble hydrophilic coating composition comprising (A) water-insoluble hydrophilic copolymer having a water absorbing capacity of 10 to 250% by weight comprising (a) 5 to 30% by weight of at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and citraconic acid, . (b) 5 to 90% by weight of at least one member selected from the group consisting of (i) amino group-containing ethyl-enically unsaturated monomer having the general formula I:
CH2=CRl 1OOR2N~ ( I ) wherein R4 , R2 is alkylene having 1 - 4 carbon atoms, and R3 and R4 are alkyl having 1 - 4 carbon atoms and (ii) diacetone acrylamide, (c) a balance of at least one ethylenically unsaturated ' monomer selected from the group consisting of . (i) a monomer having the general formula II:
; CH2=CR5 COOR6 (II) wherein R5 is H or CH3 and R6 is alkyl having 1 - 12 carbon atoms and (ii) a monomer having the general formula III: `-CH2=CR7 COO(R8O)H (III) ~ ¢~ ' 10~1390 ' wherein R7 is H or CH3 and . R8 is alkylene having 2 - 3 carbon atoms and (B) 5 to 20~ by weight, based on the weight of said copolymer, of a crosslinking agent.
In-the present invention, the above problems have been solved by means of a coating of a copolymer obtained by copolymerizing a monomer mixture containing 5 to 30, preferably 8 to 15% by weight of a carboxyl group-containing ethylenically unsaturated monomer, 5 to 90, preferably 10 to 80% by weight of an amino group-containing ethylenically unsaturated monomer and a balance of the total 100% by weight ;:
of another monomer capable of copolymerizing with the aforesaid monomers. While the mechanism of regulating the water 15 absorbing capacity of the resulting copolymer is uncertain, ~ -it is essential that both carboxyl groups and amino groups -~
- coexist with each other in a polymerization system and the coexistence of the both groups makes it possible to regulate the water absorbing capacity of coating freely within the range from 10% by weight to 250% by weight. It will be ~-: worthy of special mention that there may be employed as :~
solvent for the copolymer not only polar solvents but also :
non-polar solvents, such as toluene, xylene and like aromatics and ethyl acetate, butyl . .
- 4a -~09139~J
acetate and like esters. Thus~ in accordance with the pre-sent invention, as crosslinking agent there may be used isocyanates which are unusable in polar solvents. In addi-` tion, the amino groups contained in the polymeric system makes it easy to completely react with an epoxy compound atroom temperature. And, the resulting coating exhibits a good adhesion to substrates.
The hydrophilic copolymer in accordance with the present invention is useful as, e.g., coatings for underwater constructions and anti-fogging coatings.
The term "underwater construction" so far as used in this specification means watercraft and underwater static structures. The term "watercraft" means àll sorts of movable structures such as, e.g., sailboats, yachts, motor boats, canoes, water skis, surfboards, ocean liners, tugboats, tan-ker and warship. The term underwater static structures means quay wall, pier, bridge and other various at least partly submerged fixed structures. The surfaces of the underwater constructions may be formed of metals, wood, plastics, concrete and other solids. The coating in accordance with the present invention is of great value as ship coating which imparts to such movable or fixed structures resistance against fouling by barnacle, algae, slime, oyster, ascidian and like marine ~; living things.
As anti-fogging coating it may be applied to the surfaces of e.g., glasses, sunglasses, goggles, mirror, win-- dowpane and aluminum sash. A transfer paper may be prepared by forming a layer of the hydrophilic copolymer on a substrate and then applying thereover a layer of a water soluble paste and a layer of a dye paste. A planographic plate may be prepared by forming a layer of the hydrophilic copolymer on ~ - 5 -,.
~091390 an aluminum plate or like base material and applying there-over a photosensiti~e layer.
It is essential for the copolymer of the present invention that it is water insoluble and has a water absorb-ing capacity of 10 to 250, preferably 40 to 150~ by weight.
The polymer has an intrinsic viscosity of 0.05 to 3.0, preferably 0.08 to 2.0, most preferably 0.1 to 1.5 when a solution dissolved 1 g of the polymer into 25 ml of methyl-; cellosolve is measured by an Ostwald viscometer at a tempera-ture of 20C.
The carboxyl group-containing ethylenically unsatu~
rated monomer suitably used in the practice of the present ; invention includes, e.g., acrylic acid, metnacrylic acid, maleic anhydride, fumaric acid, itaconic acid and citraconic acid, and may be used in an amount of 5 to 30, preferably 8 to 15% by weight. In amounts less than 5% by weight, the coating film formed is insufficient in adhesion to substrate while, on the other hand, in amounts exceeding 30% by weight, the coating film becomes readily peelable when swollen.
The amino group-containing ethylenically unsaturated monomer includes, e.g., acrylamide, methacrylamide; N-methyl acrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopr acrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylmide, N-isopropylmeth-25 acrylamide, N-butylmethacrylamide and like N-alkylated acrylamides and methacrylamides; diacetoneacrylamide;
2-aminoethyl acrylate, 2-aminoethyl methacrylate, 3-aminopro-pyl acrylate, 3-aminopropyl methacrylate, 4-aminobutyl acry-late, 4-aminobutyl methacrylate and like aminoalkyl acrylates 30 and methacrylates; dimethylaminoethyl acrylate, dimethylamin-oethyl methacrylate, dimethylaminopropyl acrylate, dimethy-l(J~ 9() : laminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminoethyl acrylate, diethylam~xethyl methacrylate, diethylaminopropyl acrylate, diethylami-nopropyl methacrylate, dibuti~laminoethyl acrylate, di~ltylaminoethyl methacrylate,~3-(dimethyiam noethy )-2-hy~ro~ypropyl acr,-late, 3-dimethy-laminoethyl)-2-hydroxypropyl methacrylate and like alkylamin-oalkyl acrylates and methacrylates; p-aminostyrene, o-aminos-tyrene, 2-amino-4-vinyltoluene, morpholinoethyl acrylate, 2-vinylpyridine, 4-vinylpyridine, lO-aminodecyl vinyl ether, N-methylaminoethyl vinyl ether, N-2-ethylhexylaminoethyl vinyl ether and like amino vinyl ethers. The amino monomer may be used in an amount of 5 to 90, preferably lO to 80% by weight. In amounts of less than 5~ by weight, hydraulic re-sistance reducing effect is unobtainable because of a low water absorbing capacity of at most 10% by weight of the resulting coating.
It is necessary to use a monomer which is copoly-merizable with the aforesaid monomers, in an amount of the balance of 100% by weight. The copolymerizable monomer -20 includes, e.g., methyl acrylate, ethyl acrylate, n-propyl -acrylate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate and like alkyl- and cycloalkyl acrylates and -methacrylates;
methoxyethyl acrylate, methoxyethyl methacrylate, methoxy-propyl acrylate, methoxypropyl methacrylate, ethoxyethyl acrylate, etho-xyethyl methacrylate and like alkoxyalkyl acrylates and methacrylates;
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-: '~
, i~
~0913~0 hydroxypropyl acrylate, 3-hydroxypropyl methacrylate and like hydroxyalkyl acrylates and methacrylates; diethyleneglycol monoacrylate, diethyleneglycol monomethacrylate, triethylene-glycol monoacrylate, triethyleneglycol monomethacrylate and like hydroxyalkoxyalkyl acrylates and methacrylate; 2-chloro-
It is necessary to use a monomer which is copoly-merizable with the aforesaid monomers, in an amount of the balance of 100% by weight. The copolymerizable monomer -20 includes, e.g., methyl acrylate, ethyl acrylate, n-propyl -acrylate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate and like alkyl- and cycloalkyl acrylates and -methacrylates;
methoxyethyl acrylate, methoxyethyl methacrylate, methoxy-propyl acrylate, methoxypropyl methacrylate, ethoxyethyl acrylate, etho-xyethyl methacrylate and like alkoxyalkyl acrylates and methacrylates;
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-: '~
, i~
~0913~0 hydroxypropyl acrylate, 3-hydroxypropyl methacrylate and like hydroxyalkyl acrylates and methacrylates; diethyleneglycol monoacrylate, diethyleneglycol monomethacrylate, triethylene-glycol monoacrylate, triethyleneglycol monomethacrylate and like hydroxyalkoxyalkyl acrylates and methacrylate; 2-chloro-
3-hydroxypropyl acrylate, 2-chloro-3-hydroxypropyl methacry-late and like chloro-hydroxyalkyl acrylates and methacrylates;
and glycidyl methacrylate.
The coating film in accordance with the present invention which lowers the hydraulic resistance of a coated ship bottom-moving underwater and possesses an undercoated or incorporated anti-fouling capacity is stable for a long period of time as it is, though better results are obtained when the coating film is crosslinked. The crosslinked copoly-mer is effective especially in such a case where in the coat-ing film there is incorporated an anti-fouling agent or like additive because the crosslinked copolymer ensures the ever-lasting adhesion of a coating film to anunderwater construc-tion and the stability of the coating film.
The crosslinking agent may be used in an amount of 0.01 to 20, preferably 5 to 20~ by weight based on the total weight of the aforesaid monomer mixture. However, it should not be used in such an amount as to result in a coating film having a water absorbing capacity of 10% by weight or less ... .
because such a low water absorbing capacity accompanies decrease in effect of lowering hydraulic frictional resistance.
The crosslinking agent may be exemplified by, e.g., isocya-nates, such as tolylene diisocyanate, hexamethylene diisocy-anate, lysine diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate and high molecular polyisocya-nates derived from such diisocyanates, e.g. Coronate* L and * trade mark 105 13~0 Coronate* HL produced by Nippon Polyurethane K.K., Desmodur*
L, Desmodur* ~, Desmodur* IL and Desmodur* HL
produced by Bayer A.G.; and polyepoxides havlng terminal epoxy groups, such as standard polyepoxides obtained by reac-tion of bisphenol A and epichlorohydrine of the following general formula C 2 ~ CHCH2~ O- ~ -G _ ~ 2j 2 ~ O
2C~ CH2 wherein n is O or positive integer, sold under trade name of Epicoat* 828, 827, 1004 and 1009 by Shell Chemical Co., poly- -epoxides derived from novolak of the following general formula , - .
~: O ~ IH2 O ~ 1~2 ~ CH2 CH C~ \ CH
CH2 11 ~2 1I H2 ,, O O O
~2 ~ ~ ~
wher2in n is a positi~e integer, sold under a trade name of Epicoat* 152 by Shell Chemical Co., and polyepoxides having :.
more than 2 terminal epoxy groups such as a compound of the following formula $
* trade marks g _ :
` ~ 109139(J
., ( C~2 - ~C~z - o -~3 /~ o - C~ C~ C~z CH - CH
C~2 ~ C~ICH2 - O~ - C~2C - CH2 O O
sold under a trade name of ~pon* 1031 by Shell Chemical Co., and 4,4-diaminodiphenylpropane tetraglycidyl ether. Of course, there may be used as crosslinking agent ammonium bichromate and melamine resins.
The hydrophilic copolymer of the present invention ~- may be prepared in any PolYmerizatîon processes, i.e. in solution polymerization in a suitable solvent~ in suspension `- polymerization or in cast or mass polymerization followed by dissolving the resulting high molecular product in a suitable solvent. The polymerization is carried out, in the presence of a radical polymerization catalyst, at temperatures usually of 50 to 140C, preferably of 80 to 100C, for 1 to 20 hours, preferably 9 to 12 hours. The radical polymerization catalyst ,: , .
includes, e.g., tert-butyl peroctoate, benzoyl peroxide, iso-propyl percarbonate, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide and azobisisobutylonitrile, and may be used in an amount, based on the total weight of the above monomer mixture, usually of 0.01 to 5.0%, preferably Y of 0.1 to 1.0% by weight.
` 20 For the purpose of keeping the ship bottoms, a coating of the hydrophilic copolymer of the present invention may be applied over a conventional anti-fouling agent provided *trade mark .~ ~
` 1091~39V
that it allows sufficient penetration of the anti-fouling agent.
For the preparation of a coating capable of pre-venting an underwater construction from fouling by marine lining things, there may be incorporated in the coating composition of the present invention any of the conventional inorganic or organic anti-fouling agents, cuprous oxide, copper powder, mercuric oxide, cuprous oxide-mercuric oxide (e.g. 3:1 mercurous chloride), organotin compounds including triphenyltin chloride, triphenyltin bromide, tri p-cresyltin chloride, triethyltin chloride, tributyltin chloride, phenyl diethyltin fluoride, tri (p-chlorophenyltin) chloride, tri (m-chlorophenyltin) chloride, dibutyl ethyltin bromide, dibutyloctyltin bromide, tricyclohexyltin chloride, tri-ethyltin stearate, tributyltin stearate, triethyltin fluoride,tributyltin fluoride, diphenyl ethyltin, chloride, diphenyl ethyltin fluoride, triphenyltin hydroxide, triphenyltin thiocyanate, triphenyltin trichloroacetate, tributyltin acetate, tributyltin neodecanoate, tributyltin neopentanoate, trioctyltin neodecanoate, tributyltin oxide, trioctyltin ~.. .
; oxide, triphenyltin fluoride, tripropyltin oleate, tripropyl-tin neodecanoate, tributyltin laurate, tributyltin octanoate, tributyltin dimethyl carbonate, tributyltin resinate tributy-ltin chromate, amyldiethyltin neodecanoate, tributyltin naphthenate tributyltin isooctylmercaptoacetate, bis-Itri-butyltin) oxalate, bis-(tributyltin) malonate, bis-(tribut-yltin) adipate, bis-(tributyltin) carbomate, organo lead compounds, e.g. triphenyl lead acetate, triphenyl lead -30 stearate, triphenyl lead neodecanoate, triphenyl lead oleate, triphenyl lead chloride, triphenyl lead laurate, triethyl lead oleate, triethyl lead acetate, triethyl lead stearate, 11~91390 triret}i~l lea~ stearate, triph~nyl lead bromide, tri~henyl lead fluoride, organic co~x~ds incluaing 10,10' -oxybisphenox~azine (SA-546), 1, 2, 3-trichloro-4,6-dinitrobenzene, hexachlorophene, dichloro-diphenyl trichloroethane (DDT~, phenol mercuric acetate,tetrachloroisophthalonitrile, bis-(n-propyl-sulfonyl) ethy-lene, tetramethylthiurum sulfide, zinc methylthio-carbamate, etc. The anti-fouling agent is incorporated in the manner such that it can be liberated from the coating film of hydro-philic copolymers. The necessary amount of the anti-fouling agent in the coating film varies depending on the agent used and the degree of fouling which a coated underwater construc-tion e~x~nters in its use, in general it is used in amounts within the range of 2 to 200% by weight based on the resin solid though it may be used in a small amount as 0.1% by weight. The anti-fouling agent should not be incorporated in such a large amount as to hinder the hydrophilic copolymer forming a continuous coating film. Of course, there may be ; incorporated in the composition of the present invention conventional pigments and loading fillers, such as titanium dioxide, red lead, red iron oxide, talcum powder, aluminum silicate, acid clay, pumice, zinc oxide, calcium carbonate and aluminum dust.
The coating of the present invention is usually applied from an organic solvent solution to the surface of a structure to be coated. The solvent suitably used includes, e.g., methanol, ethanol, propanol, isopropancl, butanol and like lower alcohols; ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether, ethyleneglycol monopropyl ether, ethyleneglycol monobutyl ether and like ethyleneglycol monalkyl ethers; dimethylformamide, dimethylsulfoxide, ~' ' lV91390 N-methylpyrrolidone and like organic solvents; and mixtures thereof and therewith water. In certain cases, there may be used aromatic and aliphatic hydrocarbons, such as benzene, toluene, xylene and hexane, and petrolic mixed solvents. The 5 organic solvent solution contains the aforesaid copolymer in -a concentration usually of 1 to 70% by weight, preferably of 20 to 50~ by weight.
The coating of the present invention exhibits a sufficient adhesion to an anti-fouling top coating previously applied to a surface ofan underwater construction protected by a corrosion resisting coating such as an epoxy resin-, - vinyl resin- or chlorinated rubber-based coating material, ; and to unsaturated polyester resin-glass fiber laminates.
The thickness of a coating applied is varied depend-ing on the composition used and the coating process employed, ;~ within a range usually of 10 to 500 microns, preferably of from 30 to 200 microns. The coating is applied to surfaces of underwater constructions by brush coating, dip coating, spray coating, roller coating or any of the other coating processes.
~; The present invention will be illustrated in more detail by the following examples in which all parts are by weight unless otherwise noted.
- Example In a flask equipped with a thermometer, a stirrer and a reflux condenser there were charged 10 parts of meth-acrylic acid, 40 parts of dimethylaminoethyl methacrylate, 50 parts of lauryl methacrylate and 400 parts of butyl acetate.
After addition of 0.5 part of azobisisobutylonitrile as cata-lyst, the charge was heated at 75C for about 10 hours to obtain a syrupy liquid. To 100 g of the syrup was added 14 g . .
. .
-~0~1390 of Coronate L, a polyisocyanate of a solid content 75% and isocyanate content 12.7 to 13.7% supplied by Nippon Poly-urethane K.K. The mixture was thoroughly stirred and then applied to an aluminum disc of a diameter of 20 cm precoated with Ravax* #2, a ship bottom paint supplied by Chugoku Toryo K.K., to obtain an about 30 microns thick coating film.
~hen the coated disc was submerged in the sea for a long period of time there was observed no growth of barnacles and seaweeds. The disc was rotated in water at a rate of 2,400 r.p.m. for determination of hydraulic friction resistance.
The test result indicated that the coating film of the pre-sent invention lowered the friction resistance by about 8%.
In the test there was not observed peeling of the coating film.
, 15 On the other hand, the coating composition was cast on a chromium plated panel to form an about 0.5 mm thick coating. The coating was dried under reduced pressure for 48 hours, then weighed and submerged for a week to deter-mine the water absorbing capacity. The capacity determined was about 80%. [~ ] = 0.27.
Example 2 Into the same flask as used in Example 1, there were charged 10 parts of methacrylic acid, 20 parts of dimethylaminoethyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 60 parts of lauryl methacrylate and 400 parts - of xylene. The charge was then added with 0.5 part of azobisisobutylonitrile as catalyst and heated at about 75 C
; for about 10 hours to obtain a syrupy liquid of a polymer content of 20%. The syrupy liquid was added in the same proportion with Example 1 Coronate HL, a polyisocyanate of a solid content about 75~ and an isocyanate content 12 * Trade Mark .:
~0~13.90 to 13~ supplied by Nippon Polyurethane ~.K., and processed in the same manner as in Example 1, The resulting coating exhibited a water absorbing capacity of 60% and a friction resistance reduction of about 7%. The coating was of a good adhesion and did not peel during durability test at all.
[~ ] = 0.21.
Example 3 Into the same flask as used in Example 1 there were charged 10 parts of acrylic acid, 20 parts of dimethylamino-ethyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of diacetoneacrylamide and 50 parts of butyl acrylate and as solvent 300 parts of isopropanol. The charge was then added with 0.5 part of azobisisobutylonitrile and subjected to polymerization at 75C for 10 hours. The resulting syrupy liquid was added with Epicoat 1004 (Shell Chemical Co.) in the amount of 10~ based on the weight of the polymer in the syrup and the mixture was well stirred. The coating composi-tion thus obtained was subjected to the same tests as in Example 1. The friction resistance reduction was about 5.5%
and the water absorbing capacity was about 40%. [~ ]= 0.18.
Example 4 Into the same flask as in Example 1 there were charged 10 parts of methacrylic acid, 10 parts of dimethyla-minomethyl methacrylate, 10 parts of acrylamide, 10 parts of diacetoneacrylamide and 60 parts of butyl acrylate and as solvent 300 parts of a 3:7 mixture of butyl acetate and ethylcellosolve. The charge was then added with 0.5 parts of azobisisobutylonitrile as catalyst and subjected to reac-tion at 75C for 10 hours. The reaction mixture was then added with Epon 1031 (Shell Chemical Co.) in the amount corresponding to 5~ of the solid in the reaction mixture and, ~ 1091390 after thoroughly stirred, applied to a disc and subjected to the same tests as in Example 1. There was obtained a fric-tion resistance reducing effect of about 5% and the water absorbing capacity was about 40~. [~ ] = 0.26.
Example 5 Into the same flask as in Example 1 there were charged 10 parts of methacrylic acid, 40 parts of dimethyla-minomethyl methacrylate, 30 parts of diacetoneacrylamide, 20 parts of lauryl methacrylate and 300 parts of methylcello-solve as solvent. The charge was then added with 0.5 partof azobisisobutylonitrile as catalyst and subjected to reaction at 75C for 10 hours. The reaction mixture was ; then added with 5%, based on the weight of polymer in the mixture, of Epon 1031 (Shell Chemical Co.) and well stirred.
The coating composition was applied to a disc and subjected to the same tests as in Example 1. There was obtained a friction resistance reduction of about 6% and the water absorbing capacity was about 90%. [~ ] = 0.21.
Example 6 Into the same flask as used in Example 1 there ` 20 were charged 10 parts of methacrylic acid, 40 parts of dimethylaminomethyl methacrylate, 40 parts of diacetoneacry-lamide, 20 parts of lauryl methacrylate and 300 parts of ; methylcellosolve as solvent. The charge was then added with 0 5~ of azobisisobutylonitrile as catalyst and subjected to reaction at 75C for 10 hours. The reaction mixture was then added with 5%, based on the polymer content in the mix-ture, of Epon 1031 (Shell Chemical Co.) and, after thoroughly stirred, applied to a disc and subjected to the same tests as in Example 1. The friction resistance reduction was about 30 6.5 % and the water absorbing capacity was about 130%-~]=0.18.
,. .
~09139U
Control Into the same flask as in Example 1 there were charged 100 parts of 2-hydroxyethyl methacrylate, 400 parts of methylcellosolve and 0.3 part of azobisisobutylonitrile, and the mixture was subjected to reaction at 75C for about 10 hours to obtain a syrup. The syrup was then added with 2 parts of a 20 wt.% aqueous ammonium bichromate, applied to the same disc as used in Example 1 and dried in room for ~, about 24 hours. When the coated disc was revolved at a high speed in water, the last coat peeled off and the friction resistance rather increased by 3%. So, coating time was prolonged, i.e., a coated disc was dried in room for about 1 week under irradiation from a fluorescent light. In this case, there was obtained a resistance reduction of about 3% without any peeling-off of the coating.
Another specimen of the coating was heated for shortening of drying time. Heating at temperatures below lo0OC for about 60 minutes had little effect, while, when a - specimen heated at 130C for 30 minutes, was subjected to tests, the coating did not peel in rotary disc test in water and the resistance reduction was 4%. In all cases the water ;- absorbing capacity were about 40%. [~ ] =0.4.
Control 2 Into the same flask ~as used in Example 1 there were charged 40 parts of 2-hydroxyethyl methacrylate, 60 parts of butyl acrylate, 0.5 part of azobisisobutylonitrile and 300 parts of methylcellosolve, and the charge was sub-jected to reaction at 75C for 10 hours. The resulting syrup was added with 10%, based on the weight of the poly-meric content of the syrup, of Epicoat 1004 (Shell Chemical Co.) and applied to a disc in the same manner as in Example 1. When the coat disc was subjected to tests, the coating 3~U
`: swelled immediately and peeled off because of incompleteness of curing, so that it was impossible to determine the resis-tance reduction and water absorbing capacity. [~] = 0.35.
Control 3 Into the same flask as used in Example 1 there were charged 20 parts of methacrylic acid, 20 parts of 2-hydroxyethyl methacrylate, 60 parts of butyl methacrylate, 0.5 part of azobisisobutylonitrile and, as solvents, 280 7 parts of methylcellosolve and 120 parts of toluene, and the charge was subjected to reaction at 75C for 10 hours. The resulting syrup was added with 10%, based on the weight of polymer in the syrup, of Epicoat 1031 (Shell Chemical Co.) and applied to a disc. The coating film was peeled off imme-diately when immersed in water because of incompleteness of curing.
Asis known by the Controls 2 and 3, polymer or copolymer containing no amino group in its molecule cannot react at room temperature with epoxy resin. [~ ] = 0.45.
Control 4 Into the same flask as used in Example 1 there were charged 10 parts of 2-hydroxyethyl methacrylate, 40 parts of dimethylamlnoethyl methacrylate, 50 parts of butyl meth-acrylate, 0.5 part of azobisisobutylonitrile and 400 parts - of methylcellosolve and the mixture was then subjected to reaction at 75C for 10 hours. The resulting syrup was added with 10%, based on its polymer content, of Epicoat 1004 and then subjected to the tests in the same manners as in Example 1. The coating swelled highly and peeled off from a substrate immediately after start of revolution of the disc.
30 The water absorbing capacity was above 200%. [~ ]= 0.38.
10913~U
Example 7 ' The polymer solution as prepared in the procedure of Example 5 was added with 5% of a 20% solution of Epon 1031 (Shell Chemical Co.~ in methylcellosolve and applied to a sheet glass to form a coating film of an about 30 microns thickness. After completely dried by evaporation of solvent, the coating film was perfectly transparent and did not col-lect moisture when exposed over a water bath at 75C.
Example 8 Into the same flask as used in Example 1 there were charged 10 parts of methacrylic acid, 50 parts of dimethyla- ~:
minoethyl methacrylate, 20 parts of diacetoneacrylamide, 20 parts of lauryl methacrylate, 300 parts of methylcellosolve as solvent and 0.5 part of azobisisobutylonitrile as catalyst, and the mixture was subjected to reaction at 75CC for 10 hours.
The reaction mixture was added with 10% of a 20% methyl-cellosolve solution of Epon 1031 (Shell Chemical Co.) and, after thoroughly stirred, it was applied to a sheet glass in the same manner as in Example 7 to form a coating film of a thickness of about 30 microns. The coating film was not fogged at all in the same fogging test as in Example 7.
; [~ ]= 0.20.
Example 9 To a high grade thick paperof aweight of 280 g/m2 having a good thermal dimensional stability there was applied ~ a solution as prepared in Example 1 and added with Coronate - HL in the same proportions as in Example 1 to form a coating film of a weight of 10 g solid/m2 and dried at room tempera-ture for 12 hours. The water absorbing capacity of the coating film was 80%. Carboxymethylcellulose was then applied thereover to form a paste layer of a weight of 45 g solid/m2 1~91390 and dried at 15QC for 1 minute~ Over the paste layer of the sheet thus obtained there were applied five color pastes, each being prepared by kneading a reactive dye, sodium algi-nate and a reducing agent with water, through five photo-engraved flat screens in turn 5 times to obtain five-colored transfer paper, the reactive dyes being those as ordinarily used in transfer paper. The transfer paper thus obtained was superposed on a 100% cotton knit cloth in the manner such that the printed surface of the transfer paper was in contact with the surface of the cloth. Over the back of the cloth there was layed a non-woven fabric of a moisture content of 150% and then a heat resistant water-proof paper, and the assembly was pressed at a temperature of 140C, at 20 g/cm2, ; for 50 seconds by means of an electrically heated presser to transfer the printed color layers to the cotton cloth. During the hot press, the color layers in the transfer paper complet-ely transferred to the cotton cloth. The printed cloth was dry heated at 150C for 60 seconds to fix the colors, then - washed with water to remove the paste and, finally, treated with a color fixing agent, soaked in hot water at 70 to 80C
for 15 minutes and dried in air. An apparel made out of the dyed cloth so obtained was worn for the total number of days of 30 and washed 20 times during the wearing test. The colored pattern on the cloth withstood the test without any change.
Example 10 Into the same flask as used in Example 1 there were charged 10 parts of methacrylic acid, 40 parts of dimethyla-' minoethyl methacrylate, 30 parts of diacetoneacrylamide, 20 parts of butyl acrylate and 300parts of methylcellosolve as solvent.The mixture was then added with 0.5 part of azobisisobutylo-390 :`
nitrile as catalyst and subjected to reaction at 75C for 10 hours. The reaction mixture was then added with 5%, based on its weight, of a 20% methylcellosolve solution of Epon 1031 (Shell Chemical Co.) and, after thoroughly stirred, it was applied to a 0.15 mm thick aluminum plate to form a dried coating film of a thickness of 30 microns. On the other hand, 360 parts of toluene diisocyanate was added and reacted with - 400 parts of polyethyleneglycol 400 at 140C for 30 minutes.
After cooling, the mixture was added with 260 parts of 2-hydroxyethyl methacrylate and 0.21 part of p-benzoquinone and subjected to reaction at 40C for 24 hours to obtain an unsaturated acrylic urethane resin (I). The resin (I) was a very viscous liquid at room temperature. A photosensitive composition prepared by mixing 50 parts of the resin (I) with 50 parts of a commercially available cellulose phthalate and 1 part of benzoin ethyl ether was uniformly applied over the coated surface of the aforesaid aluminum plate and dried to form a photosensitive layer of a thickness of about 2 microns.
On the photosensitive plate there was superposed a photo film and the assembly was set in a vacuum printing frame and exposed for 1 minute to a high pressure mercury lamp located 35 cm apart therefrom. The exposed plate was ; developed by means of a 1% aqueous diethanolamine solution, washed with water and dried to obtain a planographic printing plate.
The printing plate gave clear-cut printed matters of a very high dimensional preciseness on off-set printing.
The printing durability of the plate was 100,000 sheets or more and it was unnecessary to strictly control the water feed compared with the conventional printing plates.
[~] = 0.27.
.
., l~J91390 Example ll Into the same flask as used in Example l there were charged lO parts of methacrylic acid, 30 parts of dimethylaminoethyl methacrylate and 300 parts of methyl-cellosolve as solvent. The mixture was then added with 0.5part of azobisisobutylonitrile and subjected to reaction at 75C for lO hours. The solution was then added with 0.5 part of tetramethyltiuram disulfide and 0.5 part of ethyl p-hydroxysalicylate to obtain a coating or impregnating com-position suitable for anti-fungus impregnation of wood and sterilizing coating of wall. [~ ] = 0.15.
Control 5 Into the same flask as in Example l there were charged 3 parts of methacrylic acid, 40 parts of dimethy-laminoethyl methacrylate, 27 parts of lauryl methacrylate, 30 parts of diacetone acrylamide, 300 parts of methylcello-solve as a solvent and 0.5 part of azobisisobutylonitrile as a catalyst, and the mixture was subjected to polymerization - at 75C for about 10 hours to obtain a homogeneous syrup.
The syrup was then added with 10%, based on the weight of the polymeric content of the syrup, of Epon 1031 (Shell Chemical Co.) and applied to a disc in the s-ame manner as Example l. The coating film was swollen and peeled off immediately when immersed in water. The water absorbing capacity was about 60%. [~ ] =0.25.
Control 6 Into the same flask as in Example l, there were charged 35 parts of methacrylic acid, 50 parts of dimethyla-minoethyl methacrylate, 15 parts of lauryl methacrylate, 300 parts of methylcellosolve as a solvent and 0.5 part of azobisisobutylonitrile as a catalyst, and the mixture was ~`;
lV~13~) subjeeted to polymerization at 75C for about 8 hours. After finishing the polymerization the reaction product was cooled down to precipitate a copolymer, so about 600 parts of methyl-cellosolve was added into it to obtain a syrupyliquid. The syrup was then added with 10%, based on the weight of the polymeric eontent of the syrup, of Epon 1031 (Shell Chemical Co.) znd applied to a dise in the same manner as Example 1.
The eoating film swelled remarkably and peeled off immediately from the dise when the dise was rotated. The water absorbing eapaeity was more than 200%. [~ ] = 0.50.
and glycidyl methacrylate.
The coating film in accordance with the present invention which lowers the hydraulic resistance of a coated ship bottom-moving underwater and possesses an undercoated or incorporated anti-fouling capacity is stable for a long period of time as it is, though better results are obtained when the coating film is crosslinked. The crosslinked copoly-mer is effective especially in such a case where in the coat-ing film there is incorporated an anti-fouling agent or like additive because the crosslinked copolymer ensures the ever-lasting adhesion of a coating film to anunderwater construc-tion and the stability of the coating film.
The crosslinking agent may be used in an amount of 0.01 to 20, preferably 5 to 20~ by weight based on the total weight of the aforesaid monomer mixture. However, it should not be used in such an amount as to result in a coating film having a water absorbing capacity of 10% by weight or less ... .
because such a low water absorbing capacity accompanies decrease in effect of lowering hydraulic frictional resistance.
The crosslinking agent may be exemplified by, e.g., isocya-nates, such as tolylene diisocyanate, hexamethylene diisocy-anate, lysine diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate and high molecular polyisocya-nates derived from such diisocyanates, e.g. Coronate* L and * trade mark 105 13~0 Coronate* HL produced by Nippon Polyurethane K.K., Desmodur*
L, Desmodur* ~, Desmodur* IL and Desmodur* HL
produced by Bayer A.G.; and polyepoxides havlng terminal epoxy groups, such as standard polyepoxides obtained by reac-tion of bisphenol A and epichlorohydrine of the following general formula C 2 ~ CHCH2~ O- ~ -G _ ~ 2j 2 ~ O
2C~ CH2 wherein n is O or positive integer, sold under trade name of Epicoat* 828, 827, 1004 and 1009 by Shell Chemical Co., poly- -epoxides derived from novolak of the following general formula , - .
~: O ~ IH2 O ~ 1~2 ~ CH2 CH C~ \ CH
CH2 11 ~2 1I H2 ,, O O O
~2 ~ ~ ~
wher2in n is a positi~e integer, sold under a trade name of Epicoat* 152 by Shell Chemical Co., and polyepoxides having :.
more than 2 terminal epoxy groups such as a compound of the following formula $
* trade marks g _ :
` ~ 109139(J
., ( C~2 - ~C~z - o -~3 /~ o - C~ C~ C~z CH - CH
C~2 ~ C~ICH2 - O~ - C~2C - CH2 O O
sold under a trade name of ~pon* 1031 by Shell Chemical Co., and 4,4-diaminodiphenylpropane tetraglycidyl ether. Of course, there may be used as crosslinking agent ammonium bichromate and melamine resins.
The hydrophilic copolymer of the present invention ~- may be prepared in any PolYmerizatîon processes, i.e. in solution polymerization in a suitable solvent~ in suspension `- polymerization or in cast or mass polymerization followed by dissolving the resulting high molecular product in a suitable solvent. The polymerization is carried out, in the presence of a radical polymerization catalyst, at temperatures usually of 50 to 140C, preferably of 80 to 100C, for 1 to 20 hours, preferably 9 to 12 hours. The radical polymerization catalyst ,: , .
includes, e.g., tert-butyl peroctoate, benzoyl peroxide, iso-propyl percarbonate, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide and azobisisobutylonitrile, and may be used in an amount, based on the total weight of the above monomer mixture, usually of 0.01 to 5.0%, preferably Y of 0.1 to 1.0% by weight.
` 20 For the purpose of keeping the ship bottoms, a coating of the hydrophilic copolymer of the present invention may be applied over a conventional anti-fouling agent provided *trade mark .~ ~
` 1091~39V
that it allows sufficient penetration of the anti-fouling agent.
For the preparation of a coating capable of pre-venting an underwater construction from fouling by marine lining things, there may be incorporated in the coating composition of the present invention any of the conventional inorganic or organic anti-fouling agents, cuprous oxide, copper powder, mercuric oxide, cuprous oxide-mercuric oxide (e.g. 3:1 mercurous chloride), organotin compounds including triphenyltin chloride, triphenyltin bromide, tri p-cresyltin chloride, triethyltin chloride, tributyltin chloride, phenyl diethyltin fluoride, tri (p-chlorophenyltin) chloride, tri (m-chlorophenyltin) chloride, dibutyl ethyltin bromide, dibutyloctyltin bromide, tricyclohexyltin chloride, tri-ethyltin stearate, tributyltin stearate, triethyltin fluoride,tributyltin fluoride, diphenyl ethyltin, chloride, diphenyl ethyltin fluoride, triphenyltin hydroxide, triphenyltin thiocyanate, triphenyltin trichloroacetate, tributyltin acetate, tributyltin neodecanoate, tributyltin neopentanoate, trioctyltin neodecanoate, tributyltin oxide, trioctyltin ~.. .
; oxide, triphenyltin fluoride, tripropyltin oleate, tripropyl-tin neodecanoate, tributyltin laurate, tributyltin octanoate, tributyltin dimethyl carbonate, tributyltin resinate tributy-ltin chromate, amyldiethyltin neodecanoate, tributyltin naphthenate tributyltin isooctylmercaptoacetate, bis-Itri-butyltin) oxalate, bis-(tributyltin) malonate, bis-(tribut-yltin) adipate, bis-(tributyltin) carbomate, organo lead compounds, e.g. triphenyl lead acetate, triphenyl lead -30 stearate, triphenyl lead neodecanoate, triphenyl lead oleate, triphenyl lead chloride, triphenyl lead laurate, triethyl lead oleate, triethyl lead acetate, triethyl lead stearate, 11~91390 triret}i~l lea~ stearate, triph~nyl lead bromide, tri~henyl lead fluoride, organic co~x~ds incluaing 10,10' -oxybisphenox~azine (SA-546), 1, 2, 3-trichloro-4,6-dinitrobenzene, hexachlorophene, dichloro-diphenyl trichloroethane (DDT~, phenol mercuric acetate,tetrachloroisophthalonitrile, bis-(n-propyl-sulfonyl) ethy-lene, tetramethylthiurum sulfide, zinc methylthio-carbamate, etc. The anti-fouling agent is incorporated in the manner such that it can be liberated from the coating film of hydro-philic copolymers. The necessary amount of the anti-fouling agent in the coating film varies depending on the agent used and the degree of fouling which a coated underwater construc-tion e~x~nters in its use, in general it is used in amounts within the range of 2 to 200% by weight based on the resin solid though it may be used in a small amount as 0.1% by weight. The anti-fouling agent should not be incorporated in such a large amount as to hinder the hydrophilic copolymer forming a continuous coating film. Of course, there may be ; incorporated in the composition of the present invention conventional pigments and loading fillers, such as titanium dioxide, red lead, red iron oxide, talcum powder, aluminum silicate, acid clay, pumice, zinc oxide, calcium carbonate and aluminum dust.
The coating of the present invention is usually applied from an organic solvent solution to the surface of a structure to be coated. The solvent suitably used includes, e.g., methanol, ethanol, propanol, isopropancl, butanol and like lower alcohols; ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether, ethyleneglycol monopropyl ether, ethyleneglycol monobutyl ether and like ethyleneglycol monalkyl ethers; dimethylformamide, dimethylsulfoxide, ~' ' lV91390 N-methylpyrrolidone and like organic solvents; and mixtures thereof and therewith water. In certain cases, there may be used aromatic and aliphatic hydrocarbons, such as benzene, toluene, xylene and hexane, and petrolic mixed solvents. The 5 organic solvent solution contains the aforesaid copolymer in -a concentration usually of 1 to 70% by weight, preferably of 20 to 50~ by weight.
The coating of the present invention exhibits a sufficient adhesion to an anti-fouling top coating previously applied to a surface ofan underwater construction protected by a corrosion resisting coating such as an epoxy resin-, - vinyl resin- or chlorinated rubber-based coating material, ; and to unsaturated polyester resin-glass fiber laminates.
The thickness of a coating applied is varied depend-ing on the composition used and the coating process employed, ;~ within a range usually of 10 to 500 microns, preferably of from 30 to 200 microns. The coating is applied to surfaces of underwater constructions by brush coating, dip coating, spray coating, roller coating or any of the other coating processes.
~; The present invention will be illustrated in more detail by the following examples in which all parts are by weight unless otherwise noted.
- Example In a flask equipped with a thermometer, a stirrer and a reflux condenser there were charged 10 parts of meth-acrylic acid, 40 parts of dimethylaminoethyl methacrylate, 50 parts of lauryl methacrylate and 400 parts of butyl acetate.
After addition of 0.5 part of azobisisobutylonitrile as cata-lyst, the charge was heated at 75C for about 10 hours to obtain a syrupy liquid. To 100 g of the syrup was added 14 g . .
. .
-~0~1390 of Coronate L, a polyisocyanate of a solid content 75% and isocyanate content 12.7 to 13.7% supplied by Nippon Poly-urethane K.K. The mixture was thoroughly stirred and then applied to an aluminum disc of a diameter of 20 cm precoated with Ravax* #2, a ship bottom paint supplied by Chugoku Toryo K.K., to obtain an about 30 microns thick coating film.
~hen the coated disc was submerged in the sea for a long period of time there was observed no growth of barnacles and seaweeds. The disc was rotated in water at a rate of 2,400 r.p.m. for determination of hydraulic friction resistance.
The test result indicated that the coating film of the pre-sent invention lowered the friction resistance by about 8%.
In the test there was not observed peeling of the coating film.
, 15 On the other hand, the coating composition was cast on a chromium plated panel to form an about 0.5 mm thick coating. The coating was dried under reduced pressure for 48 hours, then weighed and submerged for a week to deter-mine the water absorbing capacity. The capacity determined was about 80%. [~ ] = 0.27.
Example 2 Into the same flask as used in Example 1, there were charged 10 parts of methacrylic acid, 20 parts of dimethylaminoethyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 60 parts of lauryl methacrylate and 400 parts - of xylene. The charge was then added with 0.5 part of azobisisobutylonitrile as catalyst and heated at about 75 C
; for about 10 hours to obtain a syrupy liquid of a polymer content of 20%. The syrupy liquid was added in the same proportion with Example 1 Coronate HL, a polyisocyanate of a solid content about 75~ and an isocyanate content 12 * Trade Mark .:
~0~13.90 to 13~ supplied by Nippon Polyurethane ~.K., and processed in the same manner as in Example 1, The resulting coating exhibited a water absorbing capacity of 60% and a friction resistance reduction of about 7%. The coating was of a good adhesion and did not peel during durability test at all.
[~ ] = 0.21.
Example 3 Into the same flask as used in Example 1 there were charged 10 parts of acrylic acid, 20 parts of dimethylamino-ethyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of diacetoneacrylamide and 50 parts of butyl acrylate and as solvent 300 parts of isopropanol. The charge was then added with 0.5 part of azobisisobutylonitrile and subjected to polymerization at 75C for 10 hours. The resulting syrupy liquid was added with Epicoat 1004 (Shell Chemical Co.) in the amount of 10~ based on the weight of the polymer in the syrup and the mixture was well stirred. The coating composi-tion thus obtained was subjected to the same tests as in Example 1. The friction resistance reduction was about 5.5%
and the water absorbing capacity was about 40%. [~ ]= 0.18.
Example 4 Into the same flask as in Example 1 there were charged 10 parts of methacrylic acid, 10 parts of dimethyla-minomethyl methacrylate, 10 parts of acrylamide, 10 parts of diacetoneacrylamide and 60 parts of butyl acrylate and as solvent 300 parts of a 3:7 mixture of butyl acetate and ethylcellosolve. The charge was then added with 0.5 parts of azobisisobutylonitrile as catalyst and subjected to reac-tion at 75C for 10 hours. The reaction mixture was then added with Epon 1031 (Shell Chemical Co.) in the amount corresponding to 5~ of the solid in the reaction mixture and, ~ 1091390 after thoroughly stirred, applied to a disc and subjected to the same tests as in Example 1. There was obtained a fric-tion resistance reducing effect of about 5% and the water absorbing capacity was about 40~. [~ ] = 0.26.
Example 5 Into the same flask as in Example 1 there were charged 10 parts of methacrylic acid, 40 parts of dimethyla-minomethyl methacrylate, 30 parts of diacetoneacrylamide, 20 parts of lauryl methacrylate and 300 parts of methylcello-solve as solvent. The charge was then added with 0.5 partof azobisisobutylonitrile as catalyst and subjected to reaction at 75C for 10 hours. The reaction mixture was ; then added with 5%, based on the weight of polymer in the mixture, of Epon 1031 (Shell Chemical Co.) and well stirred.
The coating composition was applied to a disc and subjected to the same tests as in Example 1. There was obtained a friction resistance reduction of about 6% and the water absorbing capacity was about 90%. [~ ] = 0.21.
Example 6 Into the same flask as used in Example 1 there ` 20 were charged 10 parts of methacrylic acid, 40 parts of dimethylaminomethyl methacrylate, 40 parts of diacetoneacry-lamide, 20 parts of lauryl methacrylate and 300 parts of ; methylcellosolve as solvent. The charge was then added with 0 5~ of azobisisobutylonitrile as catalyst and subjected to reaction at 75C for 10 hours. The reaction mixture was then added with 5%, based on the polymer content in the mix-ture, of Epon 1031 (Shell Chemical Co.) and, after thoroughly stirred, applied to a disc and subjected to the same tests as in Example 1. The friction resistance reduction was about 30 6.5 % and the water absorbing capacity was about 130%-~]=0.18.
,. .
~09139U
Control Into the same flask as in Example 1 there were charged 100 parts of 2-hydroxyethyl methacrylate, 400 parts of methylcellosolve and 0.3 part of azobisisobutylonitrile, and the mixture was subjected to reaction at 75C for about 10 hours to obtain a syrup. The syrup was then added with 2 parts of a 20 wt.% aqueous ammonium bichromate, applied to the same disc as used in Example 1 and dried in room for ~, about 24 hours. When the coated disc was revolved at a high speed in water, the last coat peeled off and the friction resistance rather increased by 3%. So, coating time was prolonged, i.e., a coated disc was dried in room for about 1 week under irradiation from a fluorescent light. In this case, there was obtained a resistance reduction of about 3% without any peeling-off of the coating.
Another specimen of the coating was heated for shortening of drying time. Heating at temperatures below lo0OC for about 60 minutes had little effect, while, when a - specimen heated at 130C for 30 minutes, was subjected to tests, the coating did not peel in rotary disc test in water and the resistance reduction was 4%. In all cases the water ;- absorbing capacity were about 40%. [~ ] =0.4.
Control 2 Into the same flask ~as used in Example 1 there were charged 40 parts of 2-hydroxyethyl methacrylate, 60 parts of butyl acrylate, 0.5 part of azobisisobutylonitrile and 300 parts of methylcellosolve, and the charge was sub-jected to reaction at 75C for 10 hours. The resulting syrup was added with 10%, based on the weight of the poly-meric content of the syrup, of Epicoat 1004 (Shell Chemical Co.) and applied to a disc in the same manner as in Example 1. When the coat disc was subjected to tests, the coating 3~U
`: swelled immediately and peeled off because of incompleteness of curing, so that it was impossible to determine the resis-tance reduction and water absorbing capacity. [~] = 0.35.
Control 3 Into the same flask as used in Example 1 there were charged 20 parts of methacrylic acid, 20 parts of 2-hydroxyethyl methacrylate, 60 parts of butyl methacrylate, 0.5 part of azobisisobutylonitrile and, as solvents, 280 7 parts of methylcellosolve and 120 parts of toluene, and the charge was subjected to reaction at 75C for 10 hours. The resulting syrup was added with 10%, based on the weight of polymer in the syrup, of Epicoat 1031 (Shell Chemical Co.) and applied to a disc. The coating film was peeled off imme-diately when immersed in water because of incompleteness of curing.
Asis known by the Controls 2 and 3, polymer or copolymer containing no amino group in its molecule cannot react at room temperature with epoxy resin. [~ ] = 0.45.
Control 4 Into the same flask as used in Example 1 there were charged 10 parts of 2-hydroxyethyl methacrylate, 40 parts of dimethylamlnoethyl methacrylate, 50 parts of butyl meth-acrylate, 0.5 part of azobisisobutylonitrile and 400 parts - of methylcellosolve and the mixture was then subjected to reaction at 75C for 10 hours. The resulting syrup was added with 10%, based on its polymer content, of Epicoat 1004 and then subjected to the tests in the same manners as in Example 1. The coating swelled highly and peeled off from a substrate immediately after start of revolution of the disc.
30 The water absorbing capacity was above 200%. [~ ]= 0.38.
10913~U
Example 7 ' The polymer solution as prepared in the procedure of Example 5 was added with 5% of a 20% solution of Epon 1031 (Shell Chemical Co.~ in methylcellosolve and applied to a sheet glass to form a coating film of an about 30 microns thickness. After completely dried by evaporation of solvent, the coating film was perfectly transparent and did not col-lect moisture when exposed over a water bath at 75C.
Example 8 Into the same flask as used in Example 1 there were charged 10 parts of methacrylic acid, 50 parts of dimethyla- ~:
minoethyl methacrylate, 20 parts of diacetoneacrylamide, 20 parts of lauryl methacrylate, 300 parts of methylcellosolve as solvent and 0.5 part of azobisisobutylonitrile as catalyst, and the mixture was subjected to reaction at 75CC for 10 hours.
The reaction mixture was added with 10% of a 20% methyl-cellosolve solution of Epon 1031 (Shell Chemical Co.) and, after thoroughly stirred, it was applied to a sheet glass in the same manner as in Example 7 to form a coating film of a thickness of about 30 microns. The coating film was not fogged at all in the same fogging test as in Example 7.
; [~ ]= 0.20.
Example 9 To a high grade thick paperof aweight of 280 g/m2 having a good thermal dimensional stability there was applied ~ a solution as prepared in Example 1 and added with Coronate - HL in the same proportions as in Example 1 to form a coating film of a weight of 10 g solid/m2 and dried at room tempera-ture for 12 hours. The water absorbing capacity of the coating film was 80%. Carboxymethylcellulose was then applied thereover to form a paste layer of a weight of 45 g solid/m2 1~91390 and dried at 15QC for 1 minute~ Over the paste layer of the sheet thus obtained there were applied five color pastes, each being prepared by kneading a reactive dye, sodium algi-nate and a reducing agent with water, through five photo-engraved flat screens in turn 5 times to obtain five-colored transfer paper, the reactive dyes being those as ordinarily used in transfer paper. The transfer paper thus obtained was superposed on a 100% cotton knit cloth in the manner such that the printed surface of the transfer paper was in contact with the surface of the cloth. Over the back of the cloth there was layed a non-woven fabric of a moisture content of 150% and then a heat resistant water-proof paper, and the assembly was pressed at a temperature of 140C, at 20 g/cm2, ; for 50 seconds by means of an electrically heated presser to transfer the printed color layers to the cotton cloth. During the hot press, the color layers in the transfer paper complet-ely transferred to the cotton cloth. The printed cloth was dry heated at 150C for 60 seconds to fix the colors, then - washed with water to remove the paste and, finally, treated with a color fixing agent, soaked in hot water at 70 to 80C
for 15 minutes and dried in air. An apparel made out of the dyed cloth so obtained was worn for the total number of days of 30 and washed 20 times during the wearing test. The colored pattern on the cloth withstood the test without any change.
Example 10 Into the same flask as used in Example 1 there were charged 10 parts of methacrylic acid, 40 parts of dimethyla-' minoethyl methacrylate, 30 parts of diacetoneacrylamide, 20 parts of butyl acrylate and 300parts of methylcellosolve as solvent.The mixture was then added with 0.5 part of azobisisobutylo-390 :`
nitrile as catalyst and subjected to reaction at 75C for 10 hours. The reaction mixture was then added with 5%, based on its weight, of a 20% methylcellosolve solution of Epon 1031 (Shell Chemical Co.) and, after thoroughly stirred, it was applied to a 0.15 mm thick aluminum plate to form a dried coating film of a thickness of 30 microns. On the other hand, 360 parts of toluene diisocyanate was added and reacted with - 400 parts of polyethyleneglycol 400 at 140C for 30 minutes.
After cooling, the mixture was added with 260 parts of 2-hydroxyethyl methacrylate and 0.21 part of p-benzoquinone and subjected to reaction at 40C for 24 hours to obtain an unsaturated acrylic urethane resin (I). The resin (I) was a very viscous liquid at room temperature. A photosensitive composition prepared by mixing 50 parts of the resin (I) with 50 parts of a commercially available cellulose phthalate and 1 part of benzoin ethyl ether was uniformly applied over the coated surface of the aforesaid aluminum plate and dried to form a photosensitive layer of a thickness of about 2 microns.
On the photosensitive plate there was superposed a photo film and the assembly was set in a vacuum printing frame and exposed for 1 minute to a high pressure mercury lamp located 35 cm apart therefrom. The exposed plate was ; developed by means of a 1% aqueous diethanolamine solution, washed with water and dried to obtain a planographic printing plate.
The printing plate gave clear-cut printed matters of a very high dimensional preciseness on off-set printing.
The printing durability of the plate was 100,000 sheets or more and it was unnecessary to strictly control the water feed compared with the conventional printing plates.
[~] = 0.27.
.
., l~J91390 Example ll Into the same flask as used in Example l there were charged lO parts of methacrylic acid, 30 parts of dimethylaminoethyl methacrylate and 300 parts of methyl-cellosolve as solvent. The mixture was then added with 0.5part of azobisisobutylonitrile and subjected to reaction at 75C for lO hours. The solution was then added with 0.5 part of tetramethyltiuram disulfide and 0.5 part of ethyl p-hydroxysalicylate to obtain a coating or impregnating com-position suitable for anti-fungus impregnation of wood and sterilizing coating of wall. [~ ] = 0.15.
Control 5 Into the same flask as in Example l there were charged 3 parts of methacrylic acid, 40 parts of dimethy-laminoethyl methacrylate, 27 parts of lauryl methacrylate, 30 parts of diacetone acrylamide, 300 parts of methylcello-solve as a solvent and 0.5 part of azobisisobutylonitrile as a catalyst, and the mixture was subjected to polymerization - at 75C for about 10 hours to obtain a homogeneous syrup.
The syrup was then added with 10%, based on the weight of the polymeric content of the syrup, of Epon 1031 (Shell Chemical Co.) and applied to a disc in the s-ame manner as Example l. The coating film was swollen and peeled off immediately when immersed in water. The water absorbing capacity was about 60%. [~ ] =0.25.
Control 6 Into the same flask as in Example l, there were charged 35 parts of methacrylic acid, 50 parts of dimethyla-minoethyl methacrylate, 15 parts of lauryl methacrylate, 300 parts of methylcellosolve as a solvent and 0.5 part of azobisisobutylonitrile as a catalyst, and the mixture was ~`;
lV~13~) subjeeted to polymerization at 75C for about 8 hours. After finishing the polymerization the reaction product was cooled down to precipitate a copolymer, so about 600 parts of methyl-cellosolve was added into it to obtain a syrupyliquid. The syrup was then added with 10%, based on the weight of the polymeric eontent of the syrup, of Epon 1031 (Shell Chemical Co.) znd applied to a dise in the same manner as Example 1.
The eoating film swelled remarkably and peeled off immediately from the dise when the dise was rotated. The water absorbing eapaeity was more than 200%. [~ ] = 0.50.
Claims (18)
1. A water-insoluble hydrophilic coating composition comprising (A) water-insoluble hydrophilic copolymer having a water absorbing capacity of 10 to 250% by weight comprising (a) 5 to 30% by weight of at least one carboxyl group-containing ethylenically unsaturated monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and citraconic acid, (b) 5 to 90% by weight of at least one member selected from the group consisting of (i) amino group-containing ethyl-enically unsaturated monomer having the general formula I:
(I) wherein R1 is H or CH3, R2 is alkylene having 1 - 4 carbon atoms, and R3 and R4 are alkyl having 1 - 4 carbon atoms and (ii) diacetone acrylamide, (c) a balance of at least one ethylenically unsaturated monomer selected from the group consisting of (i) a monomer having the general formula II:
(II) wherein R5 is H or CH3 and R6 is alkyl having 1 - 12 carbon atoms and (ii) a monomer having the general formula III:
(III) wherein R7 is H or CH3 and R8 is alkylene having 2 - 3 carbon atoms and (B) 5 to 20% by weight, based on the weight of said copolymer, of a crosslinking agent.
(I) wherein R1 is H or CH3, R2 is alkylene having 1 - 4 carbon atoms, and R3 and R4 are alkyl having 1 - 4 carbon atoms and (ii) diacetone acrylamide, (c) a balance of at least one ethylenically unsaturated monomer selected from the group consisting of (i) a monomer having the general formula II:
(II) wherein R5 is H or CH3 and R6 is alkyl having 1 - 12 carbon atoms and (ii) a monomer having the general formula III:
(III) wherein R7 is H or CH3 and R8 is alkylene having 2 - 3 carbon atoms and (B) 5 to 20% by weight, based on the weight of said copolymer, of a crosslinking agent.
2. A composition according to Claim 1, wherein the monomer (b) is a compound of general formula:
wherein R1 is H or CH3, R2 is alkylene having 1 or 2 carbon atoms and, R3 and R4 are alkyl having 1 or 2 carbon atoms;
and/or is diacetone acrylamide.
wherein R1 is H or CH3, R2 is alkylene having 1 or 2 carbon atoms and, R3 and R4 are alkyl having 1 or 2 carbon atoms;
and/or is diacetone acrylamide.
3. A composition according to Claim 2, wherein the monomer (a) is acrylic or methacrylic acid, the monomer (b) is at least one member selected from the group consisting of (i) a monomer having the general formula:
wherein R1 is H or CH3 and R3 and R4 are alkyl having 1 - 2 carbon atoms and (ii) diacetone acrylamide and monomer (c) is at least one member selected from the group consisting of (i) a monomer having the general formula:
wherein R5 is H or CH3 and R6 is alkyl having 1 - 12 carbon atoms, and (ii) hydroxyethyl acrylate or hydroxyethyl methacrylate.
wherein R1 is H or CH3 and R3 and R4 are alkyl having 1 - 2 carbon atoms and (ii) diacetone acrylamide and monomer (c) is at least one member selected from the group consisting of (i) a monomer having the general formula:
wherein R5 is H or CH3 and R6 is alkyl having 1 - 12 carbon atoms, and (ii) hydroxyethyl acrylate or hydroxyethyl methacrylate.
4. A composition according to any one of Claims 1, 2 or 3, wherein the crosslinking agent is a compound selected from the group consisting of isocyanate compounds containing at least 2 isocyanate groups and polyepoxides containing terminal epoxy groups.
5. A composition according to any one of Claims 1, 2 or 3, wherein the crosslinking agent is a polyepoxide containing terminal epoxy groups.
6. A composition according to any one of Claims 1, 2 or 3, wherein the crosslinking agent is a polyepoxide containing terminal epoxy groups, said polyepoxide being selected from the group consisting of:
wherein n is zero or a positive integer, wherein n is a positive integer,
wherein n is zero or a positive integer, wherein n is a positive integer,
7. A composition according to any one of Claims 1, 2 or 3, wherein the units derived from the monomer (a) are present in an amount of 8 to 15% by weight and the units derived from the monomer (b) are present in an amount of 10 to 80% by weight.
8. A composition according to any one of Claims 1, 2 or 3, wherein the water absorbing capacity of the copolymer is 40 to 150% by weight.
9. A composition according to any one of Claims 1, 2 or 3, wherein the copolymer has an intrinsic viscosity, as herein defined, of 0.05 to 3Ø
10. A composition according to any one of Claims 1, 2 or 3, wherein the copolymer has an intrinsic viscosity, as herein defined, of 0.08 to 2Ø
11. A composition according to any one of Claims 1, 2 or 3, wherein the copolymer has an intrinsic viscosity, as herein defined, of 0.1 to 1.5.
12. A composition according to claim 1, in which (a) is methylacrylic acid; and (b) is dimethylaminoethylmetha-crylate.
13. A composition according to Claim 1, in which (a) is methacrylic acid; and (b) is dimethylaminomethylmetha-crylate.
14. A composition according to Claim 12 or 13, further including lauryl methacrylate as monomer (c) (i).
15. A composition according to Claim 12 or 13, further including lauryl methacrylate as monomer (c) (i) and further including 2-hydroxyethyl methacrylate as monomer (c) (ii).
16. A composition according to Claim 12 or 13, further including lauryl methacrylate as monomer (c) (i) and in which (b) also includes diacetone acrylamide.
17. A composition according to Claim 13, in which (b) further includes acrylamide and diacetone acrylamide;
and further including butyl acrylate as monomer (c) (i).
and further including butyl acrylate as monomer (c) (i).
18. A composition according to any one of Claims 1, 2 or 3, in which (a) is acrylic acid; (b) is dimethylamino-ethyl methacrylate, and diacetone acrylamide; (c) (i) is butylacrylate and (c) (ii) is 2-hydroxyethyl methacrylate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50072716A JPS5949243B2 (en) | 1975-06-17 | 1975-06-17 | Method for producing hydrophilic polymer |
| JP72716/75 | 1975-06-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091390A true CA1091390A (en) | 1980-12-09 |
Family
ID=13497342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA254,537A Expired CA1091390A (en) | 1975-06-17 | 1976-06-10 | Hydrophilic polymer |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5949243B2 (en) |
| CA (1) | CA1091390A (en) |
| DE (1) | DE2626706A1 (en) |
| DK (1) | DK268676A (en) |
| FR (1) | FR2316263A1 (en) |
| GB (1) | GB1546822A (en) |
| IT (1) | IT1065634B (en) |
| NL (1) | NL7606561A (en) |
| SE (1) | SE7606855L (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5232928A (en) * | 1975-09-10 | 1977-03-12 | Hitachi Chem Co Ltd | Compositions for use in ship bottom coatings |
| JPS5232926A (en) * | 1975-09-10 | 1977-03-12 | Hitachi Chem Co Ltd | Compositions for use in ship bottom coatings |
| JPS5232927A (en) * | 1975-09-10 | 1977-03-12 | Hitachi Chem Co Ltd | Compositions for use in ship bottom coatings |
| JPS5263225A (en) * | 1975-10-23 | 1977-05-25 | Hitachi Chem Co Ltd | Water-soluble compositions for ship bottom paints |
| JPS5461234A (en) * | 1977-10-25 | 1979-05-17 | Hitachi Chem Co Ltd | Polyurethane resin coating composition |
| DE3013912A1 (en) | 1980-04-11 | 1981-10-29 | Röhm GmbH, 6100 Darmstadt | POLYMER PRODUCTS FOR TREATING BLOSSOMS AND LEATHER |
| JPS6032860A (en) * | 1983-07-30 | 1985-02-20 | Dainippon Ink & Chem Inc | Aqueous coating composition for treating substrate |
| JPS6155163A (en) * | 1984-08-27 | 1986-03-19 | Nippon Sheet Glass Co Ltd | Coated article having both photochromic and anti-fogging properties |
| JPS6155728U (en) * | 1984-09-14 | 1986-04-15 | ||
| JPS62124156A (en) * | 1985-11-25 | 1987-06-05 | Mitsui Toatsu Chem Inc | Production of aqueous coating film |
| JPS62124155A (en) * | 1985-11-25 | 1987-06-05 | Mitsui Toatsu Chem Inc | Aqueous coating film |
| JPH0742436B2 (en) * | 1985-12-09 | 1995-05-10 | 三井東圧化学株式会社 | Method for producing aqueous coating film |
| DE3609519A1 (en) * | 1986-03-21 | 1987-09-24 | Basf Lacke & Farben | COATING AGENTS BASED ON AN ACRYLATE COPOLYMER WITH HYDROXYL, CARBOXYL AND TERTIARY AMINO GROUPS, METHOD FOR PRODUCING THE COATING AGENT AND ITS USE |
| GB8801736D0 (en) * | 1988-01-27 | 1988-02-24 | Ciba Geigy Ag | Method of making patterns |
| FR2649710A1 (en) * | 1989-07-12 | 1991-01-18 | Hoechst France | AMPHOLYTE HYDROPHILIC POLYMERS, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS ABSORBENT AGENT |
| US5395905A (en) * | 1993-01-12 | 1995-03-07 | Rohm And Haas Company | Water-soluble addition polymers of cyclohexene anhydrides |
| JP3587866B2 (en) * | 1993-08-18 | 2004-11-10 | アキレス株式会社 | Agricultural synthetic resin film |
| JP3583221B2 (en) * | 1996-02-15 | 2004-11-04 | 三洋化成工業株式会社 | Filling material for cable |
| JP6842661B2 (en) * | 2016-03-11 | 2021-03-17 | 日本エクスラン工業株式会社 | Organic solvent absorbers containing water-soluble amphoteric polymers, oil-absorbing materials and materials to be printed |
| JP6619413B2 (en) * | 2017-12-15 | 2019-12-11 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Coating composition and coating film |
| WO2022004418A1 (en) * | 2020-06-29 | 2022-01-06 | 東山フイルム株式会社 | Release sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE788302A (en) * | 1971-09-02 | 1973-03-01 | Xerox Corp | MULTI-LAYER VARIABLE SPEED PHOTORECEPTOR |
| US3907986A (en) * | 1972-12-18 | 1975-09-23 | Rit Rech Ind Therapeut | Live attenuated infectious bovine rhinotracheitis virus vaccines and preparation thereof |
-
1975
- 1975-06-17 JP JP50072716A patent/JPS5949243B2/en not_active Expired
-
1976
- 1976-06-10 CA CA254,537A patent/CA1091390A/en not_active Expired
- 1976-06-15 DE DE19762626706 patent/DE2626706A1/en not_active Withdrawn
- 1976-06-16 SE SE7606855A patent/SE7606855L/en not_active Application Discontinuation
- 1976-06-16 IT IT49973/76A patent/IT1065634B/en active
- 1976-06-16 GB GB25000/76A patent/GB1546822A/en not_active Expired
- 1976-06-16 DK DK268676A patent/DK268676A/en not_active Application Discontinuation
- 1976-06-17 FR FR7618473A patent/FR2316263A1/en active Granted
- 1976-06-17 NL NL7606561A patent/NL7606561A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51148788A (en) | 1976-12-21 |
| DE2626706A1 (en) | 1976-12-30 |
| DK268676A (en) | 1976-12-18 |
| IT1065634B (en) | 1985-03-04 |
| GB1546822A (en) | 1979-05-31 |
| FR2316263A1 (en) | 1977-01-28 |
| SE7606855L (en) | 1976-12-18 |
| FR2316263B1 (en) | 1980-09-05 |
| JPS5949243B2 (en) | 1984-12-01 |
| NL7606561A (en) | 1976-12-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |