CA1273731A - Curable aminoalkyl(meth) acrylate copolymer compositions - Google Patents
Curable aminoalkyl(meth) acrylate copolymer compositionsInfo
- Publication number
- CA1273731A CA1273731A CA000483742A CA483742A CA1273731A CA 1273731 A CA1273731 A CA 1273731A CA 000483742 A CA000483742 A CA 000483742A CA 483742 A CA483742 A CA 483742A CA 1273731 A CA1273731 A CA 1273731A
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- resin composition
- curable resin
- compound
- aminoalkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Abstract
ABSTRACT OF THE DISCLOSURE
A curable resin composition which comprises (1) a copolymer composed of an aminoalkyl acrylate and/or aminoalkyl methacrylate and an ethylenically unsaturated monomer being formu-lated with (2) a compound having at least two acryloyl groups in the molecule. The composition can be cured at low temperatures in the range of ordinary temperature to 120°C, and therefore advan-tageously used to form coating films in applications such as plas-tics, wood and concrete, where heat treatment cannot be performed.
Also, these compositions exhibit excellent adherence to various substrates and can be used as adhesives and different kinds of primers, as well. Furthermore, the composition can provide coating films that excel in terms of water resistance, weathering resistance and solvent resistance, and therefore be utilized for overpaints, etc.
A curable resin composition which comprises (1) a copolymer composed of an aminoalkyl acrylate and/or aminoalkyl methacrylate and an ethylenically unsaturated monomer being formu-lated with (2) a compound having at least two acryloyl groups in the molecule. The composition can be cured at low temperatures in the range of ordinary temperature to 120°C, and therefore advan-tageously used to form coating films in applications such as plas-tics, wood and concrete, where heat treatment cannot be performed.
Also, these compositions exhibit excellent adherence to various substrates and can be used as adhesives and different kinds of primers, as well. Furthermore, the composition can provide coating films that excel in terms of water resistance, weathering resistance and solvent resistance, and therefore be utilized for overpaints, etc.
Description
~ X73~
Curable Resin Compositions This invention relates to curable resin compositions which excel in low-temperature curing properties.
It has been proposed to provide curable resin composi-tions which are made up of combinations of polymers having at least two (meth)acryloyl groups in the molecule and polyamines having at least two primary or secondary amino groups in the mole-cule. Although the compositions are of the non-solvent type, the polymer and amino compound starting materials are both limited to low-molecular-weight compounds, thus the resulting cured materials have unsatisfactory physical properties. Besides, an attempt was made to produce linear polymers by reacting piperazine with methylenebisacrylamide in water (The U.S. Patent No. 2,759,913), but this method affords resins, which take the form of linear polymers and therefore exhibit inferior physical properties.
On the other hand, room-temperature drying types of acrylic resins are superior in transparency, gloss, weathering resistance, etc., but inferior in solvent resistance, impact resistance, adherence, etc. In order to avoid these defects a method is used which comprises copolymerization with functional monomers to produce a reactive type of resin, followed by a crosslinking reaction with a curing agent, such as epoxy and melamine resins. However, the curing of such resins requires heating at 140 to 180C for 20 to 40 minutes. This energy requirement raises the cost and also restricts the kind of usable substrates to metal articles, etc.
~737~1 242~5-525 The presenk inventors, after ex~ensive inve~tigation, found that a combination of copolymers composed of an aminoalkyl acrylate or aminoalkyl methacrylate and an ethylenically unsaturated monomPr and compounds having at least two acryloyl groups in the molecule can yield compositions with excellent low-temperature curing properties, and the finding led to completion of the present invention.
Thus, the present invention is concerned with curable resin compositions which comprises (1) a copolymer composed of an aminoalkyl acrylate and/or aminoalkyl methacrylate and an ethylenically unsa~urated monomer belng formulated with (2) a compound havlng at least two acryloyl groups.
The copolymer contains at least two amino groups and is composed of an aminoalkyl acrylate and~or aminoalkyl methacrylate represented by the formula:
CooR2NHR3 (wherein Rl is hydrogen or methyl; R2 is alkylene or hydroxyalkylene of 1 to 6 carbon atoms; R3 is hydrogen or alkyl of 1 to 6 carbon atoms) and an ethylenically unsaturated monomer.
Specific examples of the expression "aminoalkyl s 1~737~1 acrylate" or "aminoalkyl methacrylate" as used herein include acrylates, such as aminomethyl acrylate, aminoethyl acrylate, aminopropyl acrylate, amino-n-butyl acrylate, aminohexyl acrylate, N-methylaminoethyl acrylate, N-tert-butylaminoethyl acrylate and aminohydroxypropyl acrylate; and methacrylates, such as aminomethyl methacrylate, aminoethyl methacrylate, amino-n-butvl acrylate, N-methylaminoethyl methacrylate, N-tert-butylaminoethyl methacrylate and aminohydroxy-propyl methacrylate. The content of these aminoalkylacrylates or aminoalkyl methacrylates in the copolymer is normally in the range of about 1 to 40 weight ~, preferably in the range of about 2 to 20 weight %.
On the other hand, examples of the term "ethylenically unsaturated monomer" include acrylates, such as methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate; methacrylates, such as methyl methacrylate, ethyl methacrylate and n-butyl methacrylate; vinyl esters of fatty acids, such as vinyl acetate, and vinyl propionate; aliphatic monoolefins, such as ethylene, propylene and isobutene;
aromatic monoolefins, such as styrene and vinyltoluene;
and others, for example, acrylonitrile, vinyl chloride and vinyl fluoride. The copolymers, which are composed mainly of acrylates and methacrylates, among the above monomers, are favorable in terms of weathering resistance and yellowing resistance. One or two kinds of the above monomers may be contained in the copolymer, with the content in the copolymer being normally in the range of about 60 to 99 weight ~, preferably in the range of about 80 to 98 weight ~.
The copolymer being composed of the aminoalkyl acrylate and/or aminoalkyl methacrylate and ethylenically unsaturated monomer is produced by conducting polymerization in the presence of an 1~73~3~
aromatic solvent, such as toluene, or alcohol solvent, such as isopropanol, or ester solvent, such as ethyl acetate, in accordance with the conventional method, employing a radical polvmerization initator, such as those based on azo or peroxide compounds, solely or in combination with a chain transfer agent, such as mercaptanes, if necessary.
The above-described copolymer contains at least two amino groups in the molecule, with its weight average molecular weight suitably being in the range of about 1,000 to 1,000,000, preferably in the range of about 5,000 to 500,000. The copolymer is used as such, but may be ketiminized with aliphatic or cyclic ketones, such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. The ketiminized product, when used in combination with the below-described compound having at least two acryloyl groups in the molecule, can provide stable one-component compositions.
Examples of the compound (~) having at least two acryloyl groups in the molecule, which is useful for crosslinking of the above-described copolymer (1), include diacrylates, such as ethylene glycol diacrylate, propylene glycol diacrylate, tetramethylene glycol diacrylate, hexamethylene glycol diacrylate and bisacryloyloxyethylhydroxyethylisocyanurate;
triacrylates, such as glycerine triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and trisacryloyloxyethylisocyanurate, tetraacrylates, such as pentaerythritol tetracrylate, urethane acrylates made up of aliphatic or alicyclic diisocyanates or polyisocyanates formed by the reactions of excess of these diisocyanates with low-molecular-weight active compounds, such as trimethylolpropane, triethanolamine and water, and ~7;~73~
acrylates, such as hydroxyethyl acrylate and hydroxypropyl acryl-ate, acrylamides, such as methylenebisacrylamide and bisacryl-amidomethyl ether;
Reaction products of compounds having an epoxy group with acrylic acid, such as acrylic acid adduct of ethylene glycol diglycidyl ether, acrylic acid adduct of glycerine diglycidyl ether, acrylic acid adduct of bisphenol A diglycidyl ether and acrylic acid adducts of 0-cresol novolac polyglycidyl ethers; and Polyester acrylates, such as ~iacrylate of a polyester diol of succinis acid and propylene glycol, diacrylate of a poly-ester diol of phthalic acid and diethylene glycol, diacrylate of a polyester diol of tetrahydrophthalic acid and diethylene glycol and polyacrylates of polyester polyols of adipic acid and tri-methylolpropane and propylene glycol.
The maximum molecular weight per acryloyl group of the above-described compounds (2) to be used for the crosslinking is in the range of 1,000.
Among the above-described, those having the ~olecular weight of 80 to 300 are preferable. These compounds can be used either solely or as a mixture of not less than two kinds.
The proportion of the copolymer (1) and the compound (2) to be used is preferably given by the following equation:
[the number of hydrogen atoms in the amino group of (1)]/[the number of acryloyl groups in (2)] = about 0.3 to 5, particularly preferably in the range of about 0.5 to 2.
The curable resin composition of the present invention as obtained by the above procedure can be used as a solution in 3~
organic solvents, such as ethyl acetate, isopropyl alcohol, methyl ethyl ketone, toluene and xylene, and also as an emulsion formed by dispersing in water. lf necessary, other resins, such as epoxy resins, plasticisers, fillers, etc. can be - 5a -,. .
. .... .
~737~1 added.
The curable resin composition of the pre~ent invention can be cured at low temperatures in the range of ordinary temperature to 120C, and therefore advantageously used for the formation of coating films in the application fields, such as plastics, wood and concrete, where heat treatment cannot be performed.
Naturally, it can be utilized for the formation of coating films in the application fields, such as metal materials, where high temperature treatment can be effected. Also, the composition of the present invention which exhibits excellent adherence toward various kinds of substrates can be used as adhesives and different kinds of primers, as well. Furthermore, the composition of the present invention can provide coating films that excel in terms of water resistance, weathering resistance and solvent resistance, and therefore be utilized for overpaints, etc.
The reference example and examples are described below to illustrate the present invention more specifically. The terms "part" and "%" as shown in the reference example and examples denote "part by weight"
and "weight %".
Reference Example Resin (A) A 30% toluene solution of a copolymer with a weight average molecular weight of 70,000 having a copolymerization composition of 86 parts of methyl methacrylate and 14 parts of aminoethyl methacrylate.
Resin (B) A 30% toluene solution of a copolymer with a weight average molecular weight of 72,000 having a copolymerization composition of 70 parts of methyl methacrylate, 15 parts of butyl acrylate and 15 parts ~Z>7;~3~
of aminoethyl methacrylate.
Resin (C~
A 40~ toluene solution of a copolymer with a weight average molecular weight of 60,000 having a S copolymerization composition of 77 parts of methyl methacrylate, 9 parts of butyl acrylate and 14 parts of aminoethyl methacrylate.
Resin (D) A 35% toluene solution of a copolymer with a weight average molecular weight of 30,000 having a copolymerization composition of 40 parts of methyl methacrylate, 40 parts of styrene, 10 parts of butyl acrylate and 10 parts of aminoethyl methacrylate.
Resin (E~
A 30% toluene solution of a copolymer with a weight average molecular weight of 56,000 having a copolymerization composition of 77 parts of methyl methacrylate, 10 parts of butyl acrylate and 13 parts of aminoethyl acrylate.
Resin (F) A resin solution prepared by dissolving the copolymer as described under Resin (A) in methyl isobutyl ketone to conduct ketiminization, followed by ad~ustment to 30% of a resin content.
Acrylic polyol (1) A 40% toluene solution (an OH equivalent of 1450) of an acrylic copolymer with a weight average molecular weight of 70,000 having a copolymerization composition of 30 parts of methyl methacrylate, 20 parts of styrene, 30 parts of butyl acrylate and 20 parts of hydroxyethyl acrylate.
Acr~lic polyol (2) Acrydic*A-801 (produced by Dai-Nippon Ink &
Chemicals Inc.; with an OH equivalent of 1120).
Blocked isocyanate * Trade ~ark 7;~1 A 60~ ethyl acetate/methyl isobutyl ketone (1/1) solution (an NCO equi~alent of 445) of a blocked isocyanate prepared by blocking a po]yisocyanate ~ormed by the reaction between 1 mole of trimethylolpropane and 3 moles of hexamethylene diisocyanate with methyl ethyl ketoxime.
Polyisocyanate A biurettized product of hexamethylene diisocyanate. (Takenate*D-165N produced by Takeda Chemical Industries, Ltd.; with an NCO equivalent of 180).
Example 1 A 56 parts portion (as a solid content) of Resin (A), along with 40 parts of titanium dioxide, was allowed to undergo dispersion with a ball mill, and 4 parts of trimethylolpropane triacrylate was added to the dispersion. The mixture was spray-coated onto a mild steel plate to a thickness of baked coating film of 40 to 50 ~m, followed by baking at 80C for 30 min.
or at 120C for 5 min. The resulting coating film showed a pencil hardness of 3H, a 60 specular gloss of 95 and excellent solvent resistance. The coating film exhibited a gloss retention of 85% and a color of 3.0 after irradiation in an accelerated weathering test machine (manufactured by Q-Panel Co. of the U. S. A) for 1000 hours.
Example 2 The procedure of Example 1 was repeatedly carried out, except that Resin (B) and pentaerythritol triacrylate were used in place of Resin (A) and trimethylolpropane triacrylate, respectively. The coating film after being baked at 120C for 20 minutes exhibited a pencil hardness of H and excellent solvent resistance.
* I'rade Mark 7~1 Example 3 In accordance with the procedure of Example 1 except that Resin (C) was used in place of Resin (A), a paint was prepared. The coating film after being baked at 120C for 15 minutes showed a pencil hardness of 2E
and excellent solvent resistance.
Example 4 By mixing 57 parts (as a solid content) of Resin (D), 40 parts of titanium dioxide and 3 parts of trimethylolpropane triacxylate, a paint was prepared.
The coating film after being baked at 120C for 15 minutes showed a pencil hardness of H and excellent solvent resistance.
Example 5 By employing Resin (E) in place of Resin (A) in Example 1, a paint was prepared. The coating film after being baked at 120C for 10 minutes showed a pencil hardness of 2H and excellent solvent resistance.
Example 6 By mixing 93 parts of Resin (F) with 7 parts of trimethylolpropane triacrylate, a one-component resin was prepared. The resin underwent no change at 40C
over the period of not less than 2 months, and remained usable. The coating film after being baked at 80C for 30 minutes showed a pencil hardness of 2H and excellent solvent resistance.
Comparative Example 1 By mixing 14.5 parts of Acrylic polyol (1) with 4.5 parts of Blocked isocyanate, a one-component urethane resin was prepared. The resulting coating film after being baked at 140C for 20 minutes showed only unsatisfactory solvent resistance.
Example 7 By combining Resins (A) and (C) respectively with trimethylolpropane triacrylate in accordance with the ~737~1 procedure of Example 1, the compositions were prepared, and spray-coated onto mild steel plates to a thickness of baked coating films of 40 to 50 ~m, followed by curing at 120C, 80C, and ambient temperature. The S typical properties of the resulting coating films were measured, with the results being shown in Table 1.
As Comparative Example 2, there is illustrated the case of the so-called two-component urethane paint based on Acrylic polyol (2) and a polyisocyanate.
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... . .
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~ o ~1 l l ~ ~ ~D ~ ~
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Ul ~ S-l ~_) -,~ ~1 0 O
a) .,.~ G) o U ~ ~:4 ~1 ~ ~
~; 5 1 ~ O ~ ~ ~ ~-1 ~-1 :1 1~ ~r G) ~ G) O G) C~ 3- ~ ~1 1~ ~:4 ~
Curable Resin Compositions This invention relates to curable resin compositions which excel in low-temperature curing properties.
It has been proposed to provide curable resin composi-tions which are made up of combinations of polymers having at least two (meth)acryloyl groups in the molecule and polyamines having at least two primary or secondary amino groups in the mole-cule. Although the compositions are of the non-solvent type, the polymer and amino compound starting materials are both limited to low-molecular-weight compounds, thus the resulting cured materials have unsatisfactory physical properties. Besides, an attempt was made to produce linear polymers by reacting piperazine with methylenebisacrylamide in water (The U.S. Patent No. 2,759,913), but this method affords resins, which take the form of linear polymers and therefore exhibit inferior physical properties.
On the other hand, room-temperature drying types of acrylic resins are superior in transparency, gloss, weathering resistance, etc., but inferior in solvent resistance, impact resistance, adherence, etc. In order to avoid these defects a method is used which comprises copolymerization with functional monomers to produce a reactive type of resin, followed by a crosslinking reaction with a curing agent, such as epoxy and melamine resins. However, the curing of such resins requires heating at 140 to 180C for 20 to 40 minutes. This energy requirement raises the cost and also restricts the kind of usable substrates to metal articles, etc.
~737~1 242~5-525 The presenk inventors, after ex~ensive inve~tigation, found that a combination of copolymers composed of an aminoalkyl acrylate or aminoalkyl methacrylate and an ethylenically unsaturated monomPr and compounds having at least two acryloyl groups in the molecule can yield compositions with excellent low-temperature curing properties, and the finding led to completion of the present invention.
Thus, the present invention is concerned with curable resin compositions which comprises (1) a copolymer composed of an aminoalkyl acrylate and/or aminoalkyl methacrylate and an ethylenically unsa~urated monomer belng formulated with (2) a compound havlng at least two acryloyl groups.
The copolymer contains at least two amino groups and is composed of an aminoalkyl acrylate and~or aminoalkyl methacrylate represented by the formula:
CooR2NHR3 (wherein Rl is hydrogen or methyl; R2 is alkylene or hydroxyalkylene of 1 to 6 carbon atoms; R3 is hydrogen or alkyl of 1 to 6 carbon atoms) and an ethylenically unsaturated monomer.
Specific examples of the expression "aminoalkyl s 1~737~1 acrylate" or "aminoalkyl methacrylate" as used herein include acrylates, such as aminomethyl acrylate, aminoethyl acrylate, aminopropyl acrylate, amino-n-butyl acrylate, aminohexyl acrylate, N-methylaminoethyl acrylate, N-tert-butylaminoethyl acrylate and aminohydroxypropyl acrylate; and methacrylates, such as aminomethyl methacrylate, aminoethyl methacrylate, amino-n-butvl acrylate, N-methylaminoethyl methacrylate, N-tert-butylaminoethyl methacrylate and aminohydroxy-propyl methacrylate. The content of these aminoalkylacrylates or aminoalkyl methacrylates in the copolymer is normally in the range of about 1 to 40 weight ~, preferably in the range of about 2 to 20 weight %.
On the other hand, examples of the term "ethylenically unsaturated monomer" include acrylates, such as methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate; methacrylates, such as methyl methacrylate, ethyl methacrylate and n-butyl methacrylate; vinyl esters of fatty acids, such as vinyl acetate, and vinyl propionate; aliphatic monoolefins, such as ethylene, propylene and isobutene;
aromatic monoolefins, such as styrene and vinyltoluene;
and others, for example, acrylonitrile, vinyl chloride and vinyl fluoride. The copolymers, which are composed mainly of acrylates and methacrylates, among the above monomers, are favorable in terms of weathering resistance and yellowing resistance. One or two kinds of the above monomers may be contained in the copolymer, with the content in the copolymer being normally in the range of about 60 to 99 weight ~, preferably in the range of about 80 to 98 weight ~.
The copolymer being composed of the aminoalkyl acrylate and/or aminoalkyl methacrylate and ethylenically unsaturated monomer is produced by conducting polymerization in the presence of an 1~73~3~
aromatic solvent, such as toluene, or alcohol solvent, such as isopropanol, or ester solvent, such as ethyl acetate, in accordance with the conventional method, employing a radical polvmerization initator, such as those based on azo or peroxide compounds, solely or in combination with a chain transfer agent, such as mercaptanes, if necessary.
The above-described copolymer contains at least two amino groups in the molecule, with its weight average molecular weight suitably being in the range of about 1,000 to 1,000,000, preferably in the range of about 5,000 to 500,000. The copolymer is used as such, but may be ketiminized with aliphatic or cyclic ketones, such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. The ketiminized product, when used in combination with the below-described compound having at least two acryloyl groups in the molecule, can provide stable one-component compositions.
Examples of the compound (~) having at least two acryloyl groups in the molecule, which is useful for crosslinking of the above-described copolymer (1), include diacrylates, such as ethylene glycol diacrylate, propylene glycol diacrylate, tetramethylene glycol diacrylate, hexamethylene glycol diacrylate and bisacryloyloxyethylhydroxyethylisocyanurate;
triacrylates, such as glycerine triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and trisacryloyloxyethylisocyanurate, tetraacrylates, such as pentaerythritol tetracrylate, urethane acrylates made up of aliphatic or alicyclic diisocyanates or polyisocyanates formed by the reactions of excess of these diisocyanates with low-molecular-weight active compounds, such as trimethylolpropane, triethanolamine and water, and ~7;~73~
acrylates, such as hydroxyethyl acrylate and hydroxypropyl acryl-ate, acrylamides, such as methylenebisacrylamide and bisacryl-amidomethyl ether;
Reaction products of compounds having an epoxy group with acrylic acid, such as acrylic acid adduct of ethylene glycol diglycidyl ether, acrylic acid adduct of glycerine diglycidyl ether, acrylic acid adduct of bisphenol A diglycidyl ether and acrylic acid adducts of 0-cresol novolac polyglycidyl ethers; and Polyester acrylates, such as ~iacrylate of a polyester diol of succinis acid and propylene glycol, diacrylate of a poly-ester diol of phthalic acid and diethylene glycol, diacrylate of a polyester diol of tetrahydrophthalic acid and diethylene glycol and polyacrylates of polyester polyols of adipic acid and tri-methylolpropane and propylene glycol.
The maximum molecular weight per acryloyl group of the above-described compounds (2) to be used for the crosslinking is in the range of 1,000.
Among the above-described, those having the ~olecular weight of 80 to 300 are preferable. These compounds can be used either solely or as a mixture of not less than two kinds.
The proportion of the copolymer (1) and the compound (2) to be used is preferably given by the following equation:
[the number of hydrogen atoms in the amino group of (1)]/[the number of acryloyl groups in (2)] = about 0.3 to 5, particularly preferably in the range of about 0.5 to 2.
The curable resin composition of the present invention as obtained by the above procedure can be used as a solution in 3~
organic solvents, such as ethyl acetate, isopropyl alcohol, methyl ethyl ketone, toluene and xylene, and also as an emulsion formed by dispersing in water. lf necessary, other resins, such as epoxy resins, plasticisers, fillers, etc. can be - 5a -,. .
. .... .
~737~1 added.
The curable resin composition of the pre~ent invention can be cured at low temperatures in the range of ordinary temperature to 120C, and therefore advantageously used for the formation of coating films in the application fields, such as plastics, wood and concrete, where heat treatment cannot be performed.
Naturally, it can be utilized for the formation of coating films in the application fields, such as metal materials, where high temperature treatment can be effected. Also, the composition of the present invention which exhibits excellent adherence toward various kinds of substrates can be used as adhesives and different kinds of primers, as well. Furthermore, the composition of the present invention can provide coating films that excel in terms of water resistance, weathering resistance and solvent resistance, and therefore be utilized for overpaints, etc.
The reference example and examples are described below to illustrate the present invention more specifically. The terms "part" and "%" as shown in the reference example and examples denote "part by weight"
and "weight %".
Reference Example Resin (A) A 30% toluene solution of a copolymer with a weight average molecular weight of 70,000 having a copolymerization composition of 86 parts of methyl methacrylate and 14 parts of aminoethyl methacrylate.
Resin (B) A 30% toluene solution of a copolymer with a weight average molecular weight of 72,000 having a copolymerization composition of 70 parts of methyl methacrylate, 15 parts of butyl acrylate and 15 parts ~Z>7;~3~
of aminoethyl methacrylate.
Resin (C~
A 40~ toluene solution of a copolymer with a weight average molecular weight of 60,000 having a S copolymerization composition of 77 parts of methyl methacrylate, 9 parts of butyl acrylate and 14 parts of aminoethyl methacrylate.
Resin (D) A 35% toluene solution of a copolymer with a weight average molecular weight of 30,000 having a copolymerization composition of 40 parts of methyl methacrylate, 40 parts of styrene, 10 parts of butyl acrylate and 10 parts of aminoethyl methacrylate.
Resin (E~
A 30% toluene solution of a copolymer with a weight average molecular weight of 56,000 having a copolymerization composition of 77 parts of methyl methacrylate, 10 parts of butyl acrylate and 13 parts of aminoethyl acrylate.
Resin (F) A resin solution prepared by dissolving the copolymer as described under Resin (A) in methyl isobutyl ketone to conduct ketiminization, followed by ad~ustment to 30% of a resin content.
Acrylic polyol (1) A 40% toluene solution (an OH equivalent of 1450) of an acrylic copolymer with a weight average molecular weight of 70,000 having a copolymerization composition of 30 parts of methyl methacrylate, 20 parts of styrene, 30 parts of butyl acrylate and 20 parts of hydroxyethyl acrylate.
Acr~lic polyol (2) Acrydic*A-801 (produced by Dai-Nippon Ink &
Chemicals Inc.; with an OH equivalent of 1120).
Blocked isocyanate * Trade ~ark 7;~1 A 60~ ethyl acetate/methyl isobutyl ketone (1/1) solution (an NCO equi~alent of 445) of a blocked isocyanate prepared by blocking a po]yisocyanate ~ormed by the reaction between 1 mole of trimethylolpropane and 3 moles of hexamethylene diisocyanate with methyl ethyl ketoxime.
Polyisocyanate A biurettized product of hexamethylene diisocyanate. (Takenate*D-165N produced by Takeda Chemical Industries, Ltd.; with an NCO equivalent of 180).
Example 1 A 56 parts portion (as a solid content) of Resin (A), along with 40 parts of titanium dioxide, was allowed to undergo dispersion with a ball mill, and 4 parts of trimethylolpropane triacrylate was added to the dispersion. The mixture was spray-coated onto a mild steel plate to a thickness of baked coating film of 40 to 50 ~m, followed by baking at 80C for 30 min.
or at 120C for 5 min. The resulting coating film showed a pencil hardness of 3H, a 60 specular gloss of 95 and excellent solvent resistance. The coating film exhibited a gloss retention of 85% and a color of 3.0 after irradiation in an accelerated weathering test machine (manufactured by Q-Panel Co. of the U. S. A) for 1000 hours.
Example 2 The procedure of Example 1 was repeatedly carried out, except that Resin (B) and pentaerythritol triacrylate were used in place of Resin (A) and trimethylolpropane triacrylate, respectively. The coating film after being baked at 120C for 20 minutes exhibited a pencil hardness of H and excellent solvent resistance.
* I'rade Mark 7~1 Example 3 In accordance with the procedure of Example 1 except that Resin (C) was used in place of Resin (A), a paint was prepared. The coating film after being baked at 120C for 15 minutes showed a pencil hardness of 2E
and excellent solvent resistance.
Example 4 By mixing 57 parts (as a solid content) of Resin (D), 40 parts of titanium dioxide and 3 parts of trimethylolpropane triacxylate, a paint was prepared.
The coating film after being baked at 120C for 15 minutes showed a pencil hardness of H and excellent solvent resistance.
Example 5 By employing Resin (E) in place of Resin (A) in Example 1, a paint was prepared. The coating film after being baked at 120C for 10 minutes showed a pencil hardness of 2H and excellent solvent resistance.
Example 6 By mixing 93 parts of Resin (F) with 7 parts of trimethylolpropane triacrylate, a one-component resin was prepared. The resin underwent no change at 40C
over the period of not less than 2 months, and remained usable. The coating film after being baked at 80C for 30 minutes showed a pencil hardness of 2H and excellent solvent resistance.
Comparative Example 1 By mixing 14.5 parts of Acrylic polyol (1) with 4.5 parts of Blocked isocyanate, a one-component urethane resin was prepared. The resulting coating film after being baked at 140C for 20 minutes showed only unsatisfactory solvent resistance.
Example 7 By combining Resins (A) and (C) respectively with trimethylolpropane triacrylate in accordance with the ~737~1 procedure of Example 1, the compositions were prepared, and spray-coated onto mild steel plates to a thickness of baked coating films of 40 to 50 ~m, followed by curing at 120C, 80C, and ambient temperature. The S typical properties of the resulting coating films were measured, with the results being shown in Table 1.
As Comparative Example 2, there is illustrated the case of the so-called two-component urethane paint based on Acrylic polyol (2) and a polyisocyanate.
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Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A curable resin composition which comprises:
(1) a copolymer containing at least two amino groups in the molecule composed of an aminoalkyl acrylate or aminoalkyl methacrylate represented by the formula (wherein R1 is hydrogen or methyl, R2 is an alkylene or hydroxyalkylene of 1 to 6 carbon atoms, and R3 is hydrogen or alkyl of 1 to 6 carbon atoms), and an ethylenically unsaturated monomer, and (2) a compound crosslinkable with the copolymer and having at least two acryloyl groups in the molecule and a molecular weight of up to 1,000.
(1) a copolymer containing at least two amino groups in the molecule composed of an aminoalkyl acrylate or aminoalkyl methacrylate represented by the formula (wherein R1 is hydrogen or methyl, R2 is an alkylene or hydroxyalkylene of 1 to 6 carbon atoms, and R3 is hydrogen or alkyl of 1 to 6 carbon atoms), and an ethylenically unsaturated monomer, and (2) a compound crosslinkable with the copolymer and having at least two acryloyl groups in the molecule and a molecular weight of up to 1,000.
2. A curable resin composition as claimed in Claim 1, wherein the copolymer has a weight average molecular weight of about 1,000 to 1,000,000.
3. A curable resin composition as claimed in Claim 1, wherein the content of the aminoalkyl acrylate or aminoalkyl methacrylate in the copolymer is in the range of about 1 to 40 weight %.
4 A curable resin composition as claimed in Claim 1,2 or 3, wherein the ethylenically unsaturated monomer is an acrylate or methacrylate.
A curable resin composition as claimed in Claim 1,2 or 3, wherein the compound (2) has a molecular weight of 80 to 300.
6. A curable resin composition as claimed in Claim 1,2 or 3, wherein the proportion of the copolymer (1) against the compound (2) is given by the following equation: [the number of amino hydrogen atoms in (1)]/[the number of acryloyl groups in (2)] =
about 0.3 to 5.
about 0.3 to 5.
7, A curable resin composition as claimed in Claim 1,2 or 3, wherein the compound (2) is trimethylolpropane triacrylate.
8. A curable resin composition as claimed in Claim 1,2 or 3, wherein the compound (2) is pentaerythritol triacrylate.
9. A resin composition which is curable at a temperature from room temperature to 120°C and comprises:
(1) a copolymer having a weight average molecular weight of from about 1,000 to about 1,000,000, containing at least two amino groups in the molecule and being composed of:
(a) 1 to 40 weight % of aminoalkyl acrylate or aminoalkyl methacrylate monomer represented by the formula (wherein R1 is hydrogen or methyl, R2 is an alkylene or hydroxyalkylene of 1 to 6 carbon atoms, and R3 is hydrogen or alkyl of 1 to 6 carbon atoms) and (b) 60 to 99 weight % of an ethylenically unsaturated monomer selected from the class consisting of alkyl acrylates, alkyl methacrylates, vinyl esters of fatty acids, aliphatic monoolefins, aromatic monoolefins, acrylonitrile, vinyl chloride and vinyl fluoride, where the said copolymer may be in a ketiminized form with an aliphatic or aromatic ketone; and (2) a compound having at least two acryloyl groups in the molecule crosslinkable with the said copolymer and having a molecular weight not more than 1,000, wherein the proportion of the copolymer (1) and the compound (2) is given by the following equation, [the number of amino hydrogen atom in (1)]/[the number of acryloyl groups in (2)] = about 0.3 to 5.
(1) a copolymer having a weight average molecular weight of from about 1,000 to about 1,000,000, containing at least two amino groups in the molecule and being composed of:
(a) 1 to 40 weight % of aminoalkyl acrylate or aminoalkyl methacrylate monomer represented by the formula (wherein R1 is hydrogen or methyl, R2 is an alkylene or hydroxyalkylene of 1 to 6 carbon atoms, and R3 is hydrogen or alkyl of 1 to 6 carbon atoms) and (b) 60 to 99 weight % of an ethylenically unsaturated monomer selected from the class consisting of alkyl acrylates, alkyl methacrylates, vinyl esters of fatty acids, aliphatic monoolefins, aromatic monoolefins, acrylonitrile, vinyl chloride and vinyl fluoride, where the said copolymer may be in a ketiminized form with an aliphatic or aromatic ketone; and (2) a compound having at least two acryloyl groups in the molecule crosslinkable with the said copolymer and having a molecular weight not more than 1,000, wherein the proportion of the copolymer (1) and the compound (2) is given by the following equation, [the number of amino hydrogen atom in (1)]/[the number of acryloyl groups in (2)] = about 0.3 to 5.
10. The curable resin composition as claimed in claim 9, wherein the compound (2) is a member selected from the class consisting of ethylene glycol diacrylate, propylene glycol diacrylate, tetramethylene glycol diacrylate, hexamethyleneglycol diacrylate, bisacryloyloxyhydroxyethylisocyanurate, glycerine triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethylisocyanurate, and pentaerythritol tetraacrylate.
11. Curable resin composition as claimed in claim 9, wherein the copolymer (1) is in a ketiminized form with an aliphatic or aromatic ketone.
12. A method of forming a coating film on a substrate, which comprises:
coating the composition as defined in any one of claims 1 to 3 and 9 to 11 on the substrate and, keeping the coating at a temperature from room temperature to 120°C to cure the composition.
coating the composition as defined in any one of claims 1 to 3 and 9 to 11 on the substrate and, keeping the coating at a temperature from room temperature to 120°C to cure the composition.
13. The method as claimed in claim 12, wherein the coated substrate is heated at a temperature of from 80 to 120°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12568884A JPS6123615A (en) | 1984-06-18 | 1984-06-18 | Curable resin composition |
| JP125688/1984 | 1984-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1273731A true CA1273731A (en) | 1990-09-04 |
Family
ID=14916222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000483742A Expired CA1273731A (en) | 1984-06-18 | 1985-06-12 | Curable aminoalkyl(meth) acrylate copolymer compositions |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4613652A (en) |
| EP (1) | EP0167042B2 (en) |
| JP (1) | JPS6123615A (en) |
| CA (1) | CA1273731A (en) |
| DE (1) | DE3565111D1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01268770A (en) * | 1988-04-20 | 1989-10-26 | Nippon Shokubai Kagaku Kogyo Co Ltd | Photopolymerizable coating agent |
| US4880849A (en) * | 1988-03-14 | 1989-11-14 | Ppg Industries, Inc. | UV coatings containing chlorinated polyolefins, method of curing, and coated substrates therefrom |
| US4833038A (en) * | 1988-03-14 | 1989-05-23 | Ppg Industries, Inc. | UV curable coatings containing oxalanilide stabilizers, method of curing, and coated substrates therefrom |
| US4942204A (en) * | 1988-08-15 | 1990-07-17 | The University Of Akron | Amphiphilic networks |
| US5270120A (en) * | 1988-12-20 | 1993-12-14 | Ciba-Geigy Corporation | Data carrying laminate |
| CA2030062A1 (en) * | 1989-11-20 | 1991-05-21 | Koichiro Saeki | Curable resin composition |
| US5310813A (en) * | 1990-08-24 | 1994-05-10 | Toagosei Chemical Industry Co., Ltd. | Thermosetting coating resin and process for producing the same |
| DE4138093B4 (en) * | 1990-11-20 | 2004-08-12 | Dainippon Ink And Chemicals, Inc. | Use of a composition for reinforcement |
| GB9112141D0 (en) * | 1991-06-05 | 1991-07-24 | Ici Resins Bv | Aqueous coating compositions |
| US6503307B1 (en) | 1999-04-27 | 2003-01-07 | Canon Kabushiki Kaisha | Ink set, printing method, ink, printed article, printing apparatus, ink cartridge, recording unit, and process of forming polymeric compound films |
| US7332218B1 (en) * | 1999-07-14 | 2008-02-19 | Eic Laboratories, Inc. | Electrically disbonding materials |
| US20080196828A1 (en) * | 1999-07-14 | 2008-08-21 | Gilbert Michael D | Electrically Disbonding Adhesive Compositions and Related Methods |
| DE60103092T2 (en) | 2000-02-10 | 2005-04-28 | Nippon Shokubai Co., Ltd. | Amino group-containing polymer (salt) and its method of preparation |
| US20070269659A1 (en) * | 2006-05-17 | 2007-11-22 | Eic Laboratories, Inc. | Electrically disbondable compositions and related methods |
| US9484123B2 (en) | 2011-09-16 | 2016-11-01 | Prc-Desoto International, Inc. | Conductive sealant compositions |
| MX2016016226A (en) * | 2016-12-08 | 2018-06-07 | Mexicano Inst Petrol | Demulsifiers for crude oil based on acrylic-aminoacrylic random copolymers of controlled molecular mass. |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2759913A (en) * | 1952-05-20 | 1956-08-21 | Hercules Powder Co Ltd | Copolymers of compounds containing activated ethylene double bonds with active hydrogen compounds |
| US3660537A (en) * | 1970-01-28 | 1972-05-02 | Du Pont | Graft copolymers containing allyl methacrylate and diethylaminoethyl methacrylate |
| US4353818A (en) * | 1977-06-03 | 1982-10-12 | Hercules Incorporated | Organic pigments |
| US4426483A (en) * | 1980-06-19 | 1984-01-17 | Hercules Incorporated | Organic pigments |
| DE3215513C3 (en) * | 1981-04-27 | 1994-07-14 | Hitachi Chemical Co Ltd | Photosensitive resin composition |
| JPS5930870A (en) * | 1982-08-13 | 1984-02-18 | Toray Ind Inc | Electron beam-curable coating composition |
| US4532021A (en) * | 1983-07-18 | 1985-07-30 | Desoto, Inc. | Adherent ultraviolet cured coatings |
-
1984
- 1984-06-18 JP JP12568884A patent/JPS6123615A/en active Granted
-
1985
- 1985-06-07 US US06/742,529 patent/US4613652A/en not_active Expired - Fee Related
- 1985-06-12 CA CA000483742A patent/CA1273731A/en not_active Expired
- 1985-06-14 DE DE8585107366T patent/DE3565111D1/en not_active Expired
- 1985-06-14 EP EP85107366A patent/EP0167042B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0167042B2 (en) | 1991-10-09 |
| JPH0464528B2 (en) | 1992-10-15 |
| JPS6123615A (en) | 1986-02-01 |
| US4613652A (en) | 1986-09-23 |
| EP0167042B1 (en) | 1988-09-21 |
| EP0167042A1 (en) | 1986-01-08 |
| DE3565111D1 (en) | 1988-10-27 |
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