CA1338575C - Curable resin composition - Google Patents
Curable resin compositionInfo
- Publication number
- CA1338575C CA1338575C CA000584748A CA584748A CA1338575C CA 1338575 C CA1338575 C CA 1338575C CA 000584748 A CA000584748 A CA 000584748A CA 584748 A CA584748 A CA 584748A CA 1338575 C CA1338575 C CA 1338575C
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- polymerizable unsaturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
This invention relates to a curable resin composi-tion which comprises a curable resin containing poly-merizable unsaturated group and aprotic onium-con-taining group of the formula (I) wherein R1 means a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms which may optionally be substituted by a hydroxyl, alkoxy or ester group or a halogen atom;
-W+ means where Z means a nitrogen atom or phosphorus atom and Y
means a sulfur atom; R2, R3 and R4 are the same or different and respectively mean an organic group of 1 to 14 carbon atoms, and R2 and R3, or R2, R3 and R4 may jointly form a heterocyclic group taken together with the adjacent nitrogen, phosphorus or sulfur atom.
-W+ means where Z means a nitrogen atom or phosphorus atom and Y
means a sulfur atom; R2, R3 and R4 are the same or different and respectively mean an organic group of 1 to 14 carbon atoms, and R2 and R3, or R2, R3 and R4 may jointly form a heterocyclic group taken together with the adjacent nitrogen, phosphorus or sulfur atom.
Description
~ 338575 CURABLE RESIN COMPOSITION
This invention relates to a curable resin composition.
When a resin having at least one unsaturated group is to be cured or hardened by heating, it has been common practice to add a radical polymerization catalyst or a polythiol to the resin to thereby cause radical addition polymerization leading to crosslinking of the resin. However, this technique has its drawbacks: the storage stability of the curable resin composition is poor and the curing of the resin surface is inhibited by oxygen in air. As an alternative to the above technique, a method has been developed which comprises reacting an active hydrogen-containing compound with the polymerizable unsaturated group in the manner of Michael addition in the presence of a basic catalyst to thereby facilitate curing. This method has also its drawbacks: the resin composition has poor storage stability and the basic catalyst retained in the cured product decreases the water resistance of the cured product.
Accordingly, it is an object of the invention to provide 2 curzble resin cor,position free o' the above drawbacks.
~' ~ nother object of the ir~ventlon is to provide a curable resin composition having good storage sta-bility.
A further object of the invention is to provide a curable resin composition having good curability.
A still further object of the invention is to provide a curable resin composition capable of giving a cured product with good water resistance.
Other objects and advantages of the invention will become apparent as the following description proceeds.
The present invention thus provides a curable resin composition which comprises a curable resin containing polymerizable unsaturated group and aprotic onium-containing group of the formula -CH-CH2-W O CORl (I) OH
wherein Rl means a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms which may optionally be substituted by a hydroxyl, alkoxy or ester group or a halogen atom;
jR2 Rl2 -W means -Z -R3 or -Y
whe-e Z ~.eans a nitrogen atom Gr phosphorus atom and Y
means a sulfur atom: R2, R3 and R4 are the same or - 3 ~. 1338575 dilferent and respectively mean an organic group of 1 to 14 carbon atoms, provided that R2 and R3, or R2, R3 and R4 may jointly form a heterocyclic group taken together with the adjacent nitrogen, phosphorus or sulfur atom as well as a curable resin composition which comprises a polymerizable unsaturated group-containing resin and a resin containing aprotic onium-containing group of the formula (I) shown above.
In accordance with one embodiment of the invention, the curable resin composition comprises a resin contain-ing polymerizable unsaturated group and aprotic onium-containing group of the formula (I) given above.
(Hereinafter, said composition is referred to as "resin composition A".) In accordance with another embodiment of the invention, the curable resin composition comprises a resin mixture composed of a resin containing polymerizable unsaturated group and a resin containing aprotic onium-containing group of the above formula (I).
(hereinafter, "resin composition B".) First, resin composition A is described in further detail.
As the resin which is a main constituent of resin composition A, any resin cont~ining at least Gne _ 4 _ 1 33 8~7 5 poly~.erizable unsaturated group and onium-containing group of the above formula (I) may be used without any particular limitaion. Thus, the resin may be any of known resins of the acrylic, polyester, urethane, alkyd, epoxy or phenolic type, for instance. Among these resins, resins of the acrylic, polyester and epoxy types are preferred. In the practice of the invention, resins containing hydroxyl group attached to primary carbon atom are particularly preferred from the curability viewpoint. The molecular weight of the resin is not specifically limited. Generally, however, the peak molecular weight of the resin as determined by gel permeation chromatography (GPC) is preferably about 250-100,000, more preferably about 400-50,000, most preferably about 500-20,000. A molecular weight exceeding the above range is not preferable since it tends to reduce coating workability.
Suitable as the above-mentioned polymerizable-unsaturated group are acryloyl, methacryloyl, ita-conoyl, maleoyl, fumaroyl, crotonoyl, acrylamido,methacrylamido, cinnamoyl, vinyl, allyl and the like groups. Among them, acryloyl and acrylamido groups are preferred.
The aprotic onium-containing group, which is represented by the above formula ~I), is required .o be _ 5 _ 1 3 3 8 5 7 5 such that the carbon atom beta ~) to the onium salt-forming nitrogen, phosphorus or sulfur atom is a secondary carbon atom having a hydroxyl group. Such aprotic oniu~-containing group is a quaternary ammonium-containing group, a quaternary phosphonium-containing group or a tertiary sulfonium-containing group.
Specific examples of the cation in the aprotic onium-containing group are as follows:
lR2 (1) - CIH - CH2 - N - R3 ( 2 ) - CH - CH2 - P - R3 IR+
(3) - IcH - CH2 - S
In the above formulas, R2, R3 and R4 are the same or different and each is an organic group of 1 to 14 carbon atoms. The organic groups R2 and R3, or R?, R3 and R4 may combinedly form, together with the adjacent nitrosen, phosphorus or sulfur atom, a heterccylic group.
The organic groups of 1 to 14 carbon atom~s which are represented by R2, R3 and R4 are not limited to any particular species provided that they will not interfere with the ionization of the ammonium, phos-phonium or sulfonium group to any substantial extent.Thus, for instance, hydrocarbon groups of 1-14 carbon atoms which may optionally contain one or more hetero atoms, for example an oxygen, sulfur and/or nitrogen atom or atoms in the form of a hydroxyl, alkoxy, sulfonyloxy or amino group, among others, are generally used.
As such hydrocarbon groups, there may be mentioned, for example, aliphatic, alicyclic or aromatic hydro-carbon groups, such as alkyl, cycloalkyl, cycloalkyl-alkyl, aryl and aralkyl groups. The alkyl group may bestraight or branched and desirably contains not more than 14 carbon atoms, in particular not more than 8 carbon atoms and includes, among others, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, pentyl, heptyl and octyl. The cycloalkyl group preferably contains not more than 14 carbon atoms r in particular 5-8 carbon atoms, and includes, among others, cyclopen-tyl, cyclohexyl, cyclohexylmethyl and cyclohexyle.hyl.
The aryl includes, zmong others, phenyl, tolyl zr.d xylyl. A suitable exzmple of the aralkyl is benzyl.
~ 7 ~ 1 3 3 8 5 7 5 As preferred examples of the oxygen-containing hydrocarbon group, there may be mentioned a hydroxyalkyl group (in particular a hydroxyl-lower-alkyl group), such as hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl or hydroxyoctyl, and an alkoxyalkyl group (in particular a lower alkoxy-lower alkyl group), such as methoxymethyl, methoxybutyl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, isopropoxy-methyl, n-butoxymethyl, iso-butoxyethyl or tert-butoxy-ethyl. As a preferred example of the sulfur-containing hydrocarbon group, there may be mentioned 2-benzene-sulfonyloxyethyl, among others. A preferred example of the nitrogen-containing hydrocarbon group is 2-(N-acet-ylamino)ethyl.
The heterocyclic group -W formed combinedly by R2 and R3, or R2, R3 and R4, together with the adjacent nitrogen, phosphorus or sulfur atom is, for example, as follows:
- ~' ~ ~ ' ~ ~ ~ ' CH3/CH=CH2 P9N ~ , - N\~
C~3 1 3 - N ,o , or - N~
~5 Pyridyl (- ~ ~) is preferred among others.
The hydrocarbon group of l to 8 carbon atoms as represented by Rl in the above formula (I), which may optionally be substituted by a hydroxyl, alkoxy or ester group or a halogen atom, there may be mentioned, for example, aliphatic, alicyclic or aromatic hydro-carbon groups, such as alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl and aralkyl groups. Among these, alkyl and alkenyl groups are preferred. The alkyl and alkenyl groups may be straight or branched and, in particular, lower ones are desirable, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, pentyl, heptyl, octyl, vinyl and 2-methylvinyl. A
typical example of the cycloalkyl is cyclohexyl. The cycloalkylalkyl group is, for example, cyclohexylmethyl or cyclohexylethyl. The aryl group includes phenyl, tolyl and xylyl, among others. A typical example of the aralkyl group is benzyl. As preferred examples of the hydroxyl-substituted hydrocarbon group, there may be mentioned hydroxyalkyl groups (in particular hydroxy-lower alkyl groups), such as hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl and hydroxyoctyl. Preferred examples of the alkoxy-substituted hydrocarbon group are alkoxyalkyl groups (in particular lower alkoxy-lower alkyl groups), such as methoxymethYl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, iso-propoxyme~yl, n-butox~ethyl, iso-butoxyethyl and tert-butoxyethyl. As preferred examples of the ester group-substit~ted hydrocarbon group, there may be mentioned lower alkoxycarbonyl-alkyl, lower alkoxycarbonylalkenyl and acyloxyalkylgroups, such as methoxycarbonylmethyl, propoxycarbonyl-ethyl, ethoxycarbonylpropyl, methoxycarbonylbutyl, methoxycarbonylethylenyl, ethoxycarbonylethylenyl, acetoxymethyl, acetoxyethyl, propionyloxymethyl and propionyloxyethyl. Preferred examples of the halogen-substituted hydrocarbon group are chloromethyl, bro-momethyl, iodomethyl, dichloromethyl, trichloromethyl, chloroethyl and chlorobutyl, among others.
Each resin molecule should have at least one polymerizable unsaturated group of the kind mentioned above. From the curability viewpoint, the polymerizable unsaturated group content is preferably within the range of 0.1 to 10 moles, more preferably within the range of 0.5 to 5 moles, most preferably within the range of -1 to 4 moles, per kilogram of the resin (as solids). When said content is lower than 0.1 mole, the resin cannot be cured to a satisfactory extent whereas when said content exceeds 10 moles, mechanical properties of the cured resin tend to decrezse unfavorablv.
The content of the above-mentioned aprctic onium-- 10- 133s575 containing group is preferably within the range of 0.01 to S moles, more pre erably within the ranse of 0.1 to 2 moles, most preferably within the range of 0.2 to 1 mole, per kilogram of the resin (as solids). The content of lower than 0.01 mole tends to cause insufficient curing. Conversely, when said content exceeds 5 moles, the water resistance of the cured product may become decreased unfavorably.
The polymerizable unsaturated group introduction into resin can be performed by using known techniques.
For instance, (i) the addition reaction between carb-oxyl group and epoxy group, (ii) the addition reaction between hydroxyl group and epoxy group, (iii) the esterification reaction between hydroxyl group and carboxyl group, (iv) the addition reaction between isocyanate group and hydroxyl group, (v) the half esterification reaction between hydroxyl group and acid - anhydride, or (vi) the ester exchange reaction between hydroxyl group and ester group can be utilized. The polymerizable unsaturated group may be contained either in a compound or a resin having such functional group as mentioned above or in both of them.
The onium-containing group introduction into resin can be carried out, for example by the method (a) or (b) mentioned below.
(2) The method comprising reactins 2 2-halogeno-l-hydro-xyethyl group-containing resin with a tertiary amine, a phosphine or a thioether in a water-immiscible inert organic solvent, then converting the halogen atom to a hydroxyl group by anion exchange and reacting the resulting resin with an organic acid.
When the compound to be reacted with the resin is a tertiary amine, the above reaction may be illustrated by the following reaction equation:
lR2 (~ - CH -- CH2 -- X + N -- R3 lR2 ' ~ - CH - CH2 - IN R3 In the above equation, ~ is the basic portion of the resin, X is a halogen atom, and R2, R3 and R4 are as defined above.
The reaction equation for the case in which a phosphine is used in lieu of the tertiary amine will be obtained by substituting P for the N in the above equation, and the reaction equation for the case in which a thioether is used in lieu of the tertiary am~ne will be obtained by substituting S for tne N in the above equation and deleting the -R4 moiety from said equation.
The above-mentioned reaction between resin and tertiary amine, phosphine or thioether is carried out under heating at about 100-150C, preferably at about 100-120C. Said reaction will be complete in about 1 to 20 hours.
The substitution of a hydroxyl group for the halogen atom can be effected, for example by passing the resin to be treated through a layer of an ordinary anion exchange resin which occurs, for example, in the form of beads.
The reaction between the thus-obtained, hydroxyl-substituted resin and an organic acid can proceed readily when both the reactants are brought into contact with each other at room temperature.
(b) The method comprising reacting a 1,2-epoxy group-containing resin simultaneously with an organic acid and any one of a tertiary amine, phosphine and thioether in a water-immiscible inert organic solvent.
When the compound to be reacted with the resin is a tertiary amine, the above reaction may be represented by the following reaction equatior.:
\ / ~
- 13 - l 3 3 8 5 7 5 - CH - CH2 - N - R3 O~ COR
In the above equation, Rl, R2, R3, R4 and ~are as defined above.
The reaction equations for the cases where a phosphine and a thioether are respectively used in lieu of the tertiary amine will be obtzined, in the same manner as mentioned above for the method (a), by substituting P for the N in the above equation or substituting S for the N and deleting the moiety -R4, respectively.
The above reaction among resin, tertiary amine and organic acid is carried out under heating at about 40-80C and will be complete in about 1 to 20 hours.
As the water-miscible inert organic solvent for use in the above methods (a) and (b), there may be mentioned, for example, ether alcohol solvents, such as ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl.ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, 21cohol solvents, such as ethanol, propanol an.d butanol, ether ester solvents, such as ethylene glycol monome ~yl e~her -- 14 - l 3 3 8 5 7 5 acetate, and ether solvents, such as dioxane, tetra-hydro~uran and diglyme. Preferred among these solvents are ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dioxane, tetrahydrofuran and diglyme.
A wide variety of known organic carboxylic acids capable of forming an anion ( OCOR1) can be used as the organic acid (HOCOR1), where R1 in the above formula (I) is a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms which may optionally be substituted by a hydroxyl, alkoxy or ester group or a halogen atom.
Specific examples are acetic acid, formic acid, tri-methylacetic acid, acrylic acid, methacrylic acid, lactic acid, hydroxyacetic acid, crotonic acid, chloro-acetic acid, maleic acid monoalkyl(C1 6) ester,fumaric acid monoalkyl(C1 6) ester, itaconic acid monoalkyl(C1 6) ester, etc. Among these, those having a dissociation constant (pKa) of at least 1 x 10 5, in particular acetic acid, formic acid and acrylic acid, are particularly preferred.
When the above-mentioned resin is an acrylic resin, the onium-containing group introduction into said resln can be carried out either by the above-men-tioned method (a) or (b) or by polymerizing, in the conventional manner, a (meth)acrylic ester monomer of the general formula CH2 1 , +
OH
wherein R5 is a hydrogen atom or a methyl group and R1 and W+ are as defined above, either alone or with at least one comonomer copolymerizable therewith.
Resin composition B is now described in futher detial.
Resin composition B contains a resin having polymerizable unsaturated group [hereinafter sometimes referred to as "resin (a)"] and a resin having aprotic onium-containing group of the kind specified above [hereinafter sometimes referred to as "resin (b)"].
As the polymerizable unsaturated group-containing resin mentioned above, any resin containing polymeriz-able unsaturated group but no onium-containing group of the above formula (I) may be used without any parti-cular limitaion. Thus, the resin may be any of knownresins of the acrylic, polyester, urethane, alkyd, epoxy or phenolic type, for instance. Among these resins, resins of the acrylic, polyester or epoxy type are preferred. In the practice of the invention, resins containing hydroxyl group are preferred and - 16 ~ 1 3 3 8 5 7 5 those with hydroxyl group attached to primary carbon atom are more preferred from the curability viewpoint.
The molecular weight of the resin is not critical.
Generally, however, the peak molecular weight of the resin as determined by gel permeation chromatography (GPC) is preferably about 250-100,000, more preferably about 400-50,000, most preferably about 500-20,000. A
molecular weigh* exceeding the above range is not preferable since it tends to reduce coating workability of the composition.
Suitable as the above-mentioned polymerizable unsaturated group are any polymerizable unsaturated groups mentioned above in relation to the resin consti-tuting resin composition A.
Each resin molecule should have at least one polymerizable unsaturated group of the kind mentioned above. From the curability viewpoint, the polymerizable unsaturated group content is preferably within the range of 0.1 to 10 moles, more preferably within the range of 0.5 to 5 moles, most preferably within the range of 1 to 4 moles, per kilogram of the resin (as solids). When said content is lower than 0.1 mole, the resin cannot be cured to a satisfactory extent, whereas when said content exceeds 10 moles, mechanical properties of the cured resin tend .o decrease unfavorably.
- 17 - l 3 3 8 5 7 5 The polymerizable unsaturated group introduction into the above-mentioned resin (a) can be performed by utilizing the same means as mentioned above for the polymerizable unsaturated group introduction into the resin constituting above-mentioned resin composition A.
As the above-mentioned resin having onium-contain-ing group, any resins having onium-containing group of the above formula (I) may be used without any parti-cul2r limitaion. The resin should preferably be compatible with the above-mentioned resin (a). Thus, the resin may be any of known resins of the acrylic, polyester, urethane, alkyd, epoxy or phenolic type, for instance. Among these resins, resins of the acrylic, polyester or epoxy type are preferred. In the practice of the invention, resins containing hydroxyl group attached to primary carbon atom are particularly preferred from the curability viewpoint. The molecular weight of the resin is not critical. Generally, how-ever, the peak molecular weight of the resin as deter-mined by GPC is preferably about 150-100,000, more preferably about 200-50,000, most preferably about 200-20,000. A molecular weight exceeding the above range is not preferable since it tends to reduce ccating workability of the composition.
Said aprotic onium-containing group is represented - 18 - l 338575 by the above formula (I) and may be any aprotic onium-containing groups mentioned above in relation to the resin constituting resin composition ~.
The content of above-mentioned aprotic onium-con-taining group is preferably within the range of 0.01 to5 moles, more preferably within the range of 0.1 to 2 moles, most preferably within the range of 0.2 to 1 mole, per kilogram of the resin (as solids). If said content is lower than 0.01 mole, insufficient curing tends to result unfavarably. On the other hand, if said content exceeds 5 moles, the water resistance of the cured product may be reduced unfavorably.
The onium-containing group introduction into said resin (b) can be conducted in the same manner as in the onium-containing group introduction into resin composition A.
The resin (b) to be used in the practice of the invention may contain polymerizable unsaturated group.
The polymerizable unsaturated group content in the resin (b) is preferably not more than 10 moles per kilogram of resin solids from a physical viewpoint of the cured product. The polymerizable unsaturated group introduction into resin (b) can be performed in the same manner as in the polymerizable unsaturated group introduct~on into resin (a).
In the practice of the invention, the proportion of resin (a) to resin (b) is preferably such that the resin (a) accounts for not more than 99.99 percent by weight!, more preferably not more than 99.9 percent by weight, on the solids basis. When the polymerizable unsaturated group content of resin (b) is less than 0.1 mole per kilogram of solids or when such group is absent in resin (b), the proportion of resin (a) is preferably within the range of 99.99 to 50 percent by weight, more preferably within the range of 99.9 to 70 percent by weight, on the solids basis, while the proportion of resin (b) is preferably within the range of 0.01 to 50 percent by weight, more preferably 0.1 to 30 percent by weight, on the same basis.
Resin compositions A and B according to the invention each may further contain various additives selected from among colored pigments, fillers, rust preventive pigments, dyes, leveling agents, antifoaming agents and antisag agents.
Resin compositions A and B according to the invention are used each in the form of a solution and/or dispersion in an organic solvent or in the form of an aqueous solution or disperslon prepared by using a w~.er-miscible solvent in the resin produc.ion step mentioned above and adding water to the resin solution obtalned or adding the resin solution to water.
Resin compositions A and B each can be cured in the following manner, for instance. Thus, the resin composition is applied, in the form of a solution or dispersion, to an article or body to be coated there-with by a conventional method, for example by spraying, brushing, roller coating or lip coating, and the coating layer is heated at a temperature not lower than 80C, preferably not lower than 100C, more preferably about 120 to 200C, preferably for a period not shorter than 5 minutes, more preferably for about 10 to 30 minutes.
In accordance with the present invention, the specific aprotic onium salt moiety contained in the resin produces the following beneficial effects: (1) it serves as a catalyst for the crosslinking curing of the resin and (2) it is eliminated from the cured product as a result of Hofmann degradation which occurs readily in the step of crosslinking curing of the resin or after crosslinking curing, whereby decrease in the water resistance of the cured product can be prevented.
Therefore, the resin composition according to the invention haf good curability as well as good storage stability. Furthermore, cured products having good water resistance can be obtained by the method accord-ing to the inventio~.
The resin composition according to the invention can be used suitably as low-temperature curable paints, among others.
The following examples are further illustrative of the present invention. "Part(s)" and "%" are "part(s) by weight" and "% by weight", respectively.
Production of resins having poly~.erizable unsatu-rated group and onium-containing group Production Example 1 A four-necked flask was charged with a mixture composed of 209 parts of Epikote*No. 154 (Shell Chemical Co.), 139 parts of ethylene glycol monobutyl ether, 84 parts of acrylic acid, 31 parts of thiodi-glycol and 0.3 part of hydroquinone, and the mixture was heated at 80C for 3 hours. The resin solution obtained [hereinafter referred to as "resin solution (A-l)] had a nonvolatile matter content of 70% and a Gardner viscosity (25C) of Z. The resin obtained had a peak molecular weight of about 1,000 as measured by GPC, and was 3.6 moles in a polymerizable unsaturated group content and 0.77 moles in an onium-containing group content, per kilosr2m of the resin.
Production ~a~ple 2 A mixtu-e of 116 parts of 2-hydroxyethyl acrylate, * Trade mark ,.,; ~
284 parts of glycidyl methacrylate, 600 parts of n-butyl methacrylate and 30 parts of azobisisobutyronitrile was added to a four-necked flask containing 667 parts of n-butyl alcohol at 130C over 3 hours to thereby effect the polymerization reaction. The flask contents were then cooled to 110C, 86 parts of methacrylic acid, 0.5 part of hydroquinone and 1 part of tetra-ethylammonium chloride were further added, and the reaction was allowed to proceed until the acid value became 0 (zero). The reaction mixture was cooled to 70C, then 60 parts of acetic acid and 89 parts of dimethylaminoethanol were further added, and the reaction was allowed to proceed for 5 hours. The thus-obtained resin solution [hereinafter referred to as "resin solution (A-2)"] had a nonvolatile matter content of 65~ and a Gardner viscosity (25C) of P.
The resin obtained had a peak molecular weight of about 12,000 as measured by GPC, and was 0.85 moles in a polymerizable unsaturated group content and 0.85 moles in an onium-containing group content, per kilogram of the resin.
Production Example 3-A carboxyl-terminated polyester having 2 peak molecular weight of about 2,000 as measured by GPC was 25synthesized by dehydration condensation at 220C of 650 - 23 ~ l 3 3 8 5 7 5 parts of itaconic acid and 248 parts of ethylene glycol.
After cooling to 110C, 93 parLs of epichlorohydrin and 727 parts of isobutanol were added to the polyester, and the mixture was heated at 110C until the acid value became 0. To the reaction mixture was further added 90 parts of pyridine, and the resultant mixture was heated at 110C for 15 hours. To the thus-obtained resin solution was added 1,000 parts of water. The chloride ion was eliminated from the resultant mixture by treatment on an anion exchange resin. The so-treat-ed solution was supplemented with 50 parts of 88%
formic acid. The aqueous resin emulsion thus obtained [hereinafter referred to as "resin solution (A-3)"] had a nonvolatile matter content of 35~ and a Gardner viscosity (25C) of B. The resin was 5.3 moles in a polymerizable unsaturated group content and 1.1 moles in an onium-containing group content, per kilogram of the resin.
Comparative Production Example 1 The procedure of Production Example 2 was followed except that 35 parts of sodium ethoxide was used in lieu of 60 parts of acetic acid and 89 parts of dimethylaminoethanol which were used in Production Example 2. Thus was obtained a resin solution [hereinafter referred to as "resin solution (A-4)"].
-- 24 - l 338575 The resin was 0.85 moles in a polymerizable unsaturated group content per kilogram of the resin.
Production of resins (a) having polymerizable unsaturated group Production Example 4 A four-necked flask was charged with a mixture of 627 parts of Epikote No. 154 (Shell Chemical Co.), 883 parts of ethylene glycol monobutyl ether, 252 parts of acrylic acid, 1 part of hydroquinone and 3 parts of tetraethylammonium bromide, and when the contents were heated at 120C for 6 hours, the acid value amounted to not more than 3 and the reaction procedure was terminat-ed. The resin solution obtained [hereinafter referred to as "resin solution (Ba-1)"] had a nonvolatile matter content of 49.5~ and a Gardner viscosity (25C) of K.
The resin had a peak molecular weight of about 900 as measured by GPC, and was 4.0 moles in a polymerizable unsaturated group content per kilogram of the resin.
Production Example 5 Polymerization was carried out by pouring a mixture of 116 parts of 2-hydroxyethyl acrylate, 284 parts of glycidyl methacrylate, 600 parts of n-butyl methacrylate and 30 parts of azobisisobutyronitrile into a four-necked flask containing 1,000 parts of n-butyl alcohol maintained at 130C over 3 hours. The polymerization mixture was cooled to 110C, then supplemented with 172 parts of methacrylic acid, 1 part of hydroquinone and 2 parts of tetraethylammonium chlo-ride, and the resultant mixture was heated at 110C
until the acid value reached 3 or less. The thus-obtained resin solution [hereinafter referred to as "resin solution (Ba-2)~ had a nonvolatile matter content of 54.0% and a Gardner viscosity (25C) of Q.
The resin had a peak molecular weight of about 10,000 as determined by GPC, and was 1.7 moles in a polymeriz-able unsaturated group content per kilogram of the resin.
Production Example 6 A carboxyl-terminated polyester was synthesized by dehydration condensation at 220C of 650 parts of itaconic acid and 248 parts of ethylene glycol, followed by addition of 754 parts of toluene. The resin solution obtained [hereinafter referred to as "resin solution (Ba-3)"] had a nonvolatile matter content of 50.0% and a Gardner viscosity (25C) of Y.
The resin had a peak molecular weight of about 700 as determined by GPC, and was 6.6 moles in a polymerizable unsaturated group content per kllogram of the resin.
Production of resins (b) having onium-containing group P~oduction Example 7 A four-necked flask was charged with a mixture of 627 parts of Epikote No. 154 (Shell Chemical Co.), 1,306 parts of ethylene glycol monobutyl ether, 252 parts of acrylic acid and 427 parts of thiodiglycol, and the mixture was heated at 80C for 3 hours. The resin solution thus obtained [hereinafter referred to as "resin solution (Bb-l)"] had a nonvolatile matter - content of 47.8% and a Gardner viscosity (25C) of P.
The resin had a peak molecular weight of about 1,000 as measured by GPC, and was 2.7 moles in an onium-con-taining content per kilogram of the resin.
Production Example 8 A four-necked flask was charged with a mixture of 900 parts of Epikote No. 1001 (Shell Chemical Co.), 204 parts of pivalic acid, 180 parts of pyridine and 1,284 parts of n-butanol, and the mixture was heated at 50C
for 10 hours. The resin solution obtained [hereinafter referred to as "resin solution (Bh-2)"] had a nonvola-tile matter content of 48.2~ and a Gardner viscosity (25C) of H. The resin had a peak molecular weight of about 1,200 as determined by GPC, and was 1.6 moles in an onium-contai~ing group content per kilogram of the resin.
Production Example 9 A four-necked flask was charged with a mixture of 93 parts of epichlorohydrin, 89 parts of dimethyl-aminoethanol and 50 parts of 88~ formic acid, and the mixture was heated at 70C for 40 minutes. The resin solution thus obtained [hereinafter referred to as "resin solution (Bb-3)"] had a nonvolatile matter content of 95% and a Gardner viscosity (25C) of T.
The resin had a peak molecular weight of about 200 25 measured by GPC, and was 4.4 moles in an onium-contain-ing group content per kilogram of the resin.
Example 1 The resin solution (A-1) obtained above in Production Example 1 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickne,ss and each film was cured by heating at 120C for 10 minutes.
Example 2 The resin solution (A-2) obtained above in Production Example 2 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C for 30 minutes.
Example 3 The resin solution (A-3) obtained above in Production Example 3 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 160C for 5 minutes.
Example 4 A mixture of 98 parts of the resin solution (Ba-l) obtained above in Production Example 4 and 2 parts of the resin solution (Bb-1) obtained above in Production Example 7 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 120C
for 30 minutes.
Example 5 A mixture of 50 parts of the resin solution (Ba-l) obtained above in Production Example 4 and 50 parts of the resin solution (Bb-l) obtained above in Production Example 7 was applied to a polished mild steel plate and a glass plate to a wet film of 100 ~m in thickness and each film was cured by heating at 120C for 30 minutes.
Example 6 A mixture of 30 parts of the resin solution (Ba-1) obtained above in Production Example 4 and 70 parts of the resin solution (Bb-l) obtained above in Production Example 7 was applied to a polished mild steel plate and a glass plate to a wet film of 100 ~m in thickness and each film was cured by heating at 120C for 30 minutes.
Example 7 A mixture of 98 parts of the resin solution (Ba-2) obtained above in Production Example 5 and 2 parts of the resin solution (Bb-2) obtained above in Production Example 8 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C
for 10 minutes.
Example 8 A mixture of 95 parts of the resin solution (Ba-2) obtained above in Production Example 5 and 5 parts of the resin solution (Bb-2) obtained above in Production Example 8 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C
for 10 minutes.
Example 9 A mixture of 70 parts of the resin solution (Ba-2) obtained above in Production Example 5 and 30 parts of the resin solution (Bb-2) obtained above in Production Example 8 was applied to a polished mild steel plate and a glass plate to obtain a wet film of lO0 ~m in 1 33857~
thickness and each film was cured by heating at 100C
for 10 minutes.
Example 10 A mixture of 99.5 parts of the resin solution (Ba-3) obtained above in Production Example 6 and 0.5 part of the resin solution (Bb-3) obtained above in Production Example 9 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 160C for 2 hours.
Example 11 A mixture of 95 parts of the resin solution (Ba-3) obtained above in Production Example 6 and 5 parts of the resin solution (Bb-3) obtained above in Production Example 9 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 160C
for 2 hours.
Example 12 A mixture of 90 parts of the resin solution (Ba-3) obtained above in Production Example 6 and 10 parts of the resin solution (Bb-3) obtained above in Production Example 9 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 160C
for 2 hours.
- 31 - l 33 8 5 ~ 5 Comparative Example 1 The resin solution (A-4) obtained above in Comparative Production Example 1 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C for 30 minutes.
Comparative Example 2 The resin solution (Ba-1) obtained above in Production Example 4 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 150C for 30 minutes.
Comparative Example 3 A mixture of 98 parts of the resin solution (Ba-1) obtained above in Production Example 4 and 2 parts of benzoyl peroxide was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 150C for 30 minutes.
Comparative Example 4 A mixture of 98 parts of the resin solution (Ba-2) obtained above in Production Example 5 and 2 parts of sodium ethylate was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C for 10 minutes.
Comparative Example 5 A mixture of 95 parts of the resin solution (Ba-3) obtained above in Production Example 3 and 5 parts of tetramethylammonium chloride was applied to a polished mild steel plate and a glass plate to a wet film of 100 ~m in thickness and each film was cured by heating at 160C for 2 hours.
The coated sheets obtained above in Examples 1 to - 12 and Comparative Examples 1 to 5 were tested in the following manner. Thus, the coated glass plates were subjected to acetone extraction test, while the coated mild steel plates were tested for water resistance.
The resin solutions used in Examples 1 to 12 and Comparative Examples 1 to 5 were tested for storage stability. The results thus obtained are shown below in Table 1.
Table 1 Immersion in Water Storage acetone resistance sta~ility Example 1 89.8% Good Good Example 2 96.0% Good Good Example 3 98.8% Good Good Example 4 90.5% Good Good Example 5 98.8% Good Good Example 6 98.5% Good Good Example 7 92.6% Good Good Example 8 94.4% Good Good Example 9 70.4% Good Good Example 10 95.9% Good Good Example 11 95.5% Good Good Example 12 91.0% Good Good Comparative 90.2% Blistering Gelation Example 1 Comparative 0% Whitening & Good Example 2 blistering Comparative 94 0% Good Gelation Example 3 Example 4 88.6% Whitening & Gelation Comparative 85.5% Blistering Good Example 5 Immersion in acetone: Unextracted film proportion after 8 hours of immersion at 40C.
ater resistance : Immersion in deionized water ~40C, 7 days).
torage stability : 40C, 3 months.
This invention relates to a curable resin composition.
When a resin having at least one unsaturated group is to be cured or hardened by heating, it has been common practice to add a radical polymerization catalyst or a polythiol to the resin to thereby cause radical addition polymerization leading to crosslinking of the resin. However, this technique has its drawbacks: the storage stability of the curable resin composition is poor and the curing of the resin surface is inhibited by oxygen in air. As an alternative to the above technique, a method has been developed which comprises reacting an active hydrogen-containing compound with the polymerizable unsaturated group in the manner of Michael addition in the presence of a basic catalyst to thereby facilitate curing. This method has also its drawbacks: the resin composition has poor storage stability and the basic catalyst retained in the cured product decreases the water resistance of the cured product.
Accordingly, it is an object of the invention to provide 2 curzble resin cor,position free o' the above drawbacks.
~' ~ nother object of the ir~ventlon is to provide a curable resin composition having good storage sta-bility.
A further object of the invention is to provide a curable resin composition having good curability.
A still further object of the invention is to provide a curable resin composition capable of giving a cured product with good water resistance.
Other objects and advantages of the invention will become apparent as the following description proceeds.
The present invention thus provides a curable resin composition which comprises a curable resin containing polymerizable unsaturated group and aprotic onium-containing group of the formula -CH-CH2-W O CORl (I) OH
wherein Rl means a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms which may optionally be substituted by a hydroxyl, alkoxy or ester group or a halogen atom;
jR2 Rl2 -W means -Z -R3 or -Y
whe-e Z ~.eans a nitrogen atom Gr phosphorus atom and Y
means a sulfur atom: R2, R3 and R4 are the same or - 3 ~. 1338575 dilferent and respectively mean an organic group of 1 to 14 carbon atoms, provided that R2 and R3, or R2, R3 and R4 may jointly form a heterocyclic group taken together with the adjacent nitrogen, phosphorus or sulfur atom as well as a curable resin composition which comprises a polymerizable unsaturated group-containing resin and a resin containing aprotic onium-containing group of the formula (I) shown above.
In accordance with one embodiment of the invention, the curable resin composition comprises a resin contain-ing polymerizable unsaturated group and aprotic onium-containing group of the formula (I) given above.
(Hereinafter, said composition is referred to as "resin composition A".) In accordance with another embodiment of the invention, the curable resin composition comprises a resin mixture composed of a resin containing polymerizable unsaturated group and a resin containing aprotic onium-containing group of the above formula (I).
(hereinafter, "resin composition B".) First, resin composition A is described in further detail.
As the resin which is a main constituent of resin composition A, any resin cont~ining at least Gne _ 4 _ 1 33 8~7 5 poly~.erizable unsaturated group and onium-containing group of the above formula (I) may be used without any particular limitaion. Thus, the resin may be any of known resins of the acrylic, polyester, urethane, alkyd, epoxy or phenolic type, for instance. Among these resins, resins of the acrylic, polyester and epoxy types are preferred. In the practice of the invention, resins containing hydroxyl group attached to primary carbon atom are particularly preferred from the curability viewpoint. The molecular weight of the resin is not specifically limited. Generally, however, the peak molecular weight of the resin as determined by gel permeation chromatography (GPC) is preferably about 250-100,000, more preferably about 400-50,000, most preferably about 500-20,000. A molecular weight exceeding the above range is not preferable since it tends to reduce coating workability.
Suitable as the above-mentioned polymerizable-unsaturated group are acryloyl, methacryloyl, ita-conoyl, maleoyl, fumaroyl, crotonoyl, acrylamido,methacrylamido, cinnamoyl, vinyl, allyl and the like groups. Among them, acryloyl and acrylamido groups are preferred.
The aprotic onium-containing group, which is represented by the above formula ~I), is required .o be _ 5 _ 1 3 3 8 5 7 5 such that the carbon atom beta ~) to the onium salt-forming nitrogen, phosphorus or sulfur atom is a secondary carbon atom having a hydroxyl group. Such aprotic oniu~-containing group is a quaternary ammonium-containing group, a quaternary phosphonium-containing group or a tertiary sulfonium-containing group.
Specific examples of the cation in the aprotic onium-containing group are as follows:
lR2 (1) - CIH - CH2 - N - R3 ( 2 ) - CH - CH2 - P - R3 IR+
(3) - IcH - CH2 - S
In the above formulas, R2, R3 and R4 are the same or different and each is an organic group of 1 to 14 carbon atoms. The organic groups R2 and R3, or R?, R3 and R4 may combinedly form, together with the adjacent nitrosen, phosphorus or sulfur atom, a heterccylic group.
The organic groups of 1 to 14 carbon atom~s which are represented by R2, R3 and R4 are not limited to any particular species provided that they will not interfere with the ionization of the ammonium, phos-phonium or sulfonium group to any substantial extent.Thus, for instance, hydrocarbon groups of 1-14 carbon atoms which may optionally contain one or more hetero atoms, for example an oxygen, sulfur and/or nitrogen atom or atoms in the form of a hydroxyl, alkoxy, sulfonyloxy or amino group, among others, are generally used.
As such hydrocarbon groups, there may be mentioned, for example, aliphatic, alicyclic or aromatic hydro-carbon groups, such as alkyl, cycloalkyl, cycloalkyl-alkyl, aryl and aralkyl groups. The alkyl group may bestraight or branched and desirably contains not more than 14 carbon atoms, in particular not more than 8 carbon atoms and includes, among others, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, pentyl, heptyl and octyl. The cycloalkyl group preferably contains not more than 14 carbon atoms r in particular 5-8 carbon atoms, and includes, among others, cyclopen-tyl, cyclohexyl, cyclohexylmethyl and cyclohexyle.hyl.
The aryl includes, zmong others, phenyl, tolyl zr.d xylyl. A suitable exzmple of the aralkyl is benzyl.
~ 7 ~ 1 3 3 8 5 7 5 As preferred examples of the oxygen-containing hydrocarbon group, there may be mentioned a hydroxyalkyl group (in particular a hydroxyl-lower-alkyl group), such as hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl or hydroxyoctyl, and an alkoxyalkyl group (in particular a lower alkoxy-lower alkyl group), such as methoxymethyl, methoxybutyl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, isopropoxy-methyl, n-butoxymethyl, iso-butoxyethyl or tert-butoxy-ethyl. As a preferred example of the sulfur-containing hydrocarbon group, there may be mentioned 2-benzene-sulfonyloxyethyl, among others. A preferred example of the nitrogen-containing hydrocarbon group is 2-(N-acet-ylamino)ethyl.
The heterocyclic group -W formed combinedly by R2 and R3, or R2, R3 and R4, together with the adjacent nitrogen, phosphorus or sulfur atom is, for example, as follows:
- ~' ~ ~ ' ~ ~ ~ ' CH3/CH=CH2 P9N ~ , - N\~
C~3 1 3 - N ,o , or - N~
~5 Pyridyl (- ~ ~) is preferred among others.
The hydrocarbon group of l to 8 carbon atoms as represented by Rl in the above formula (I), which may optionally be substituted by a hydroxyl, alkoxy or ester group or a halogen atom, there may be mentioned, for example, aliphatic, alicyclic or aromatic hydro-carbon groups, such as alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl and aralkyl groups. Among these, alkyl and alkenyl groups are preferred. The alkyl and alkenyl groups may be straight or branched and, in particular, lower ones are desirable, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, pentyl, heptyl, octyl, vinyl and 2-methylvinyl. A
typical example of the cycloalkyl is cyclohexyl. The cycloalkylalkyl group is, for example, cyclohexylmethyl or cyclohexylethyl. The aryl group includes phenyl, tolyl and xylyl, among others. A typical example of the aralkyl group is benzyl. As preferred examples of the hydroxyl-substituted hydrocarbon group, there may be mentioned hydroxyalkyl groups (in particular hydroxy-lower alkyl groups), such as hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl and hydroxyoctyl. Preferred examples of the alkoxy-substituted hydrocarbon group are alkoxyalkyl groups (in particular lower alkoxy-lower alkyl groups), such as methoxymethYl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, iso-propoxyme~yl, n-butox~ethyl, iso-butoxyethyl and tert-butoxyethyl. As preferred examples of the ester group-substit~ted hydrocarbon group, there may be mentioned lower alkoxycarbonyl-alkyl, lower alkoxycarbonylalkenyl and acyloxyalkylgroups, such as methoxycarbonylmethyl, propoxycarbonyl-ethyl, ethoxycarbonylpropyl, methoxycarbonylbutyl, methoxycarbonylethylenyl, ethoxycarbonylethylenyl, acetoxymethyl, acetoxyethyl, propionyloxymethyl and propionyloxyethyl. Preferred examples of the halogen-substituted hydrocarbon group are chloromethyl, bro-momethyl, iodomethyl, dichloromethyl, trichloromethyl, chloroethyl and chlorobutyl, among others.
Each resin molecule should have at least one polymerizable unsaturated group of the kind mentioned above. From the curability viewpoint, the polymerizable unsaturated group content is preferably within the range of 0.1 to 10 moles, more preferably within the range of 0.5 to 5 moles, most preferably within the range of -1 to 4 moles, per kilogram of the resin (as solids). When said content is lower than 0.1 mole, the resin cannot be cured to a satisfactory extent whereas when said content exceeds 10 moles, mechanical properties of the cured resin tend to decrezse unfavorablv.
The content of the above-mentioned aprctic onium-- 10- 133s575 containing group is preferably within the range of 0.01 to S moles, more pre erably within the ranse of 0.1 to 2 moles, most preferably within the range of 0.2 to 1 mole, per kilogram of the resin (as solids). The content of lower than 0.01 mole tends to cause insufficient curing. Conversely, when said content exceeds 5 moles, the water resistance of the cured product may become decreased unfavorably.
The polymerizable unsaturated group introduction into resin can be performed by using known techniques.
For instance, (i) the addition reaction between carb-oxyl group and epoxy group, (ii) the addition reaction between hydroxyl group and epoxy group, (iii) the esterification reaction between hydroxyl group and carboxyl group, (iv) the addition reaction between isocyanate group and hydroxyl group, (v) the half esterification reaction between hydroxyl group and acid - anhydride, or (vi) the ester exchange reaction between hydroxyl group and ester group can be utilized. The polymerizable unsaturated group may be contained either in a compound or a resin having such functional group as mentioned above or in both of them.
The onium-containing group introduction into resin can be carried out, for example by the method (a) or (b) mentioned below.
(2) The method comprising reactins 2 2-halogeno-l-hydro-xyethyl group-containing resin with a tertiary amine, a phosphine or a thioether in a water-immiscible inert organic solvent, then converting the halogen atom to a hydroxyl group by anion exchange and reacting the resulting resin with an organic acid.
When the compound to be reacted with the resin is a tertiary amine, the above reaction may be illustrated by the following reaction equation:
lR2 (~ - CH -- CH2 -- X + N -- R3 lR2 ' ~ - CH - CH2 - IN R3 In the above equation, ~ is the basic portion of the resin, X is a halogen atom, and R2, R3 and R4 are as defined above.
The reaction equation for the case in which a phosphine is used in lieu of the tertiary amine will be obtained by substituting P for the N in the above equation, and the reaction equation for the case in which a thioether is used in lieu of the tertiary am~ne will be obtained by substituting S for tne N in the above equation and deleting the -R4 moiety from said equation.
The above-mentioned reaction between resin and tertiary amine, phosphine or thioether is carried out under heating at about 100-150C, preferably at about 100-120C. Said reaction will be complete in about 1 to 20 hours.
The substitution of a hydroxyl group for the halogen atom can be effected, for example by passing the resin to be treated through a layer of an ordinary anion exchange resin which occurs, for example, in the form of beads.
The reaction between the thus-obtained, hydroxyl-substituted resin and an organic acid can proceed readily when both the reactants are brought into contact with each other at room temperature.
(b) The method comprising reacting a 1,2-epoxy group-containing resin simultaneously with an organic acid and any one of a tertiary amine, phosphine and thioether in a water-immiscible inert organic solvent.
When the compound to be reacted with the resin is a tertiary amine, the above reaction may be represented by the following reaction equatior.:
\ / ~
- 13 - l 3 3 8 5 7 5 - CH - CH2 - N - R3 O~ COR
In the above equation, Rl, R2, R3, R4 and ~are as defined above.
The reaction equations for the cases where a phosphine and a thioether are respectively used in lieu of the tertiary amine will be obtzined, in the same manner as mentioned above for the method (a), by substituting P for the N in the above equation or substituting S for the N and deleting the moiety -R4, respectively.
The above reaction among resin, tertiary amine and organic acid is carried out under heating at about 40-80C and will be complete in about 1 to 20 hours.
As the water-miscible inert organic solvent for use in the above methods (a) and (b), there may be mentioned, for example, ether alcohol solvents, such as ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl.ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, 21cohol solvents, such as ethanol, propanol an.d butanol, ether ester solvents, such as ethylene glycol monome ~yl e~her -- 14 - l 3 3 8 5 7 5 acetate, and ether solvents, such as dioxane, tetra-hydro~uran and diglyme. Preferred among these solvents are ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dioxane, tetrahydrofuran and diglyme.
A wide variety of known organic carboxylic acids capable of forming an anion ( OCOR1) can be used as the organic acid (HOCOR1), where R1 in the above formula (I) is a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms which may optionally be substituted by a hydroxyl, alkoxy or ester group or a halogen atom.
Specific examples are acetic acid, formic acid, tri-methylacetic acid, acrylic acid, methacrylic acid, lactic acid, hydroxyacetic acid, crotonic acid, chloro-acetic acid, maleic acid monoalkyl(C1 6) ester,fumaric acid monoalkyl(C1 6) ester, itaconic acid monoalkyl(C1 6) ester, etc. Among these, those having a dissociation constant (pKa) of at least 1 x 10 5, in particular acetic acid, formic acid and acrylic acid, are particularly preferred.
When the above-mentioned resin is an acrylic resin, the onium-containing group introduction into said resln can be carried out either by the above-men-tioned method (a) or (b) or by polymerizing, in the conventional manner, a (meth)acrylic ester monomer of the general formula CH2 1 , +
OH
wherein R5 is a hydrogen atom or a methyl group and R1 and W+ are as defined above, either alone or with at least one comonomer copolymerizable therewith.
Resin composition B is now described in futher detial.
Resin composition B contains a resin having polymerizable unsaturated group [hereinafter sometimes referred to as "resin (a)"] and a resin having aprotic onium-containing group of the kind specified above [hereinafter sometimes referred to as "resin (b)"].
As the polymerizable unsaturated group-containing resin mentioned above, any resin containing polymeriz-able unsaturated group but no onium-containing group of the above formula (I) may be used without any parti-cular limitaion. Thus, the resin may be any of knownresins of the acrylic, polyester, urethane, alkyd, epoxy or phenolic type, for instance. Among these resins, resins of the acrylic, polyester or epoxy type are preferred. In the practice of the invention, resins containing hydroxyl group are preferred and - 16 ~ 1 3 3 8 5 7 5 those with hydroxyl group attached to primary carbon atom are more preferred from the curability viewpoint.
The molecular weight of the resin is not critical.
Generally, however, the peak molecular weight of the resin as determined by gel permeation chromatography (GPC) is preferably about 250-100,000, more preferably about 400-50,000, most preferably about 500-20,000. A
molecular weigh* exceeding the above range is not preferable since it tends to reduce coating workability of the composition.
Suitable as the above-mentioned polymerizable unsaturated group are any polymerizable unsaturated groups mentioned above in relation to the resin consti-tuting resin composition A.
Each resin molecule should have at least one polymerizable unsaturated group of the kind mentioned above. From the curability viewpoint, the polymerizable unsaturated group content is preferably within the range of 0.1 to 10 moles, more preferably within the range of 0.5 to 5 moles, most preferably within the range of 1 to 4 moles, per kilogram of the resin (as solids). When said content is lower than 0.1 mole, the resin cannot be cured to a satisfactory extent, whereas when said content exceeds 10 moles, mechanical properties of the cured resin tend .o decrease unfavorably.
- 17 - l 3 3 8 5 7 5 The polymerizable unsaturated group introduction into the above-mentioned resin (a) can be performed by utilizing the same means as mentioned above for the polymerizable unsaturated group introduction into the resin constituting above-mentioned resin composition A.
As the above-mentioned resin having onium-contain-ing group, any resins having onium-containing group of the above formula (I) may be used without any parti-cul2r limitaion. The resin should preferably be compatible with the above-mentioned resin (a). Thus, the resin may be any of known resins of the acrylic, polyester, urethane, alkyd, epoxy or phenolic type, for instance. Among these resins, resins of the acrylic, polyester or epoxy type are preferred. In the practice of the invention, resins containing hydroxyl group attached to primary carbon atom are particularly preferred from the curability viewpoint. The molecular weight of the resin is not critical. Generally, how-ever, the peak molecular weight of the resin as deter-mined by GPC is preferably about 150-100,000, more preferably about 200-50,000, most preferably about 200-20,000. A molecular weight exceeding the above range is not preferable since it tends to reduce ccating workability of the composition.
Said aprotic onium-containing group is represented - 18 - l 338575 by the above formula (I) and may be any aprotic onium-containing groups mentioned above in relation to the resin constituting resin composition ~.
The content of above-mentioned aprotic onium-con-taining group is preferably within the range of 0.01 to5 moles, more preferably within the range of 0.1 to 2 moles, most preferably within the range of 0.2 to 1 mole, per kilogram of the resin (as solids). If said content is lower than 0.01 mole, insufficient curing tends to result unfavarably. On the other hand, if said content exceeds 5 moles, the water resistance of the cured product may be reduced unfavorably.
The onium-containing group introduction into said resin (b) can be conducted in the same manner as in the onium-containing group introduction into resin composition A.
The resin (b) to be used in the practice of the invention may contain polymerizable unsaturated group.
The polymerizable unsaturated group content in the resin (b) is preferably not more than 10 moles per kilogram of resin solids from a physical viewpoint of the cured product. The polymerizable unsaturated group introduction into resin (b) can be performed in the same manner as in the polymerizable unsaturated group introduct~on into resin (a).
In the practice of the invention, the proportion of resin (a) to resin (b) is preferably such that the resin (a) accounts for not more than 99.99 percent by weight!, more preferably not more than 99.9 percent by weight, on the solids basis. When the polymerizable unsaturated group content of resin (b) is less than 0.1 mole per kilogram of solids or when such group is absent in resin (b), the proportion of resin (a) is preferably within the range of 99.99 to 50 percent by weight, more preferably within the range of 99.9 to 70 percent by weight, on the solids basis, while the proportion of resin (b) is preferably within the range of 0.01 to 50 percent by weight, more preferably 0.1 to 30 percent by weight, on the same basis.
Resin compositions A and B according to the invention each may further contain various additives selected from among colored pigments, fillers, rust preventive pigments, dyes, leveling agents, antifoaming agents and antisag agents.
Resin compositions A and B according to the invention are used each in the form of a solution and/or dispersion in an organic solvent or in the form of an aqueous solution or disperslon prepared by using a w~.er-miscible solvent in the resin produc.ion step mentioned above and adding water to the resin solution obtalned or adding the resin solution to water.
Resin compositions A and B each can be cured in the following manner, for instance. Thus, the resin composition is applied, in the form of a solution or dispersion, to an article or body to be coated there-with by a conventional method, for example by spraying, brushing, roller coating or lip coating, and the coating layer is heated at a temperature not lower than 80C, preferably not lower than 100C, more preferably about 120 to 200C, preferably for a period not shorter than 5 minutes, more preferably for about 10 to 30 minutes.
In accordance with the present invention, the specific aprotic onium salt moiety contained in the resin produces the following beneficial effects: (1) it serves as a catalyst for the crosslinking curing of the resin and (2) it is eliminated from the cured product as a result of Hofmann degradation which occurs readily in the step of crosslinking curing of the resin or after crosslinking curing, whereby decrease in the water resistance of the cured product can be prevented.
Therefore, the resin composition according to the invention haf good curability as well as good storage stability. Furthermore, cured products having good water resistance can be obtained by the method accord-ing to the inventio~.
The resin composition according to the invention can be used suitably as low-temperature curable paints, among others.
The following examples are further illustrative of the present invention. "Part(s)" and "%" are "part(s) by weight" and "% by weight", respectively.
Production of resins having poly~.erizable unsatu-rated group and onium-containing group Production Example 1 A four-necked flask was charged with a mixture composed of 209 parts of Epikote*No. 154 (Shell Chemical Co.), 139 parts of ethylene glycol monobutyl ether, 84 parts of acrylic acid, 31 parts of thiodi-glycol and 0.3 part of hydroquinone, and the mixture was heated at 80C for 3 hours. The resin solution obtained [hereinafter referred to as "resin solution (A-l)] had a nonvolatile matter content of 70% and a Gardner viscosity (25C) of Z. The resin obtained had a peak molecular weight of about 1,000 as measured by GPC, and was 3.6 moles in a polymerizable unsaturated group content and 0.77 moles in an onium-containing group content, per kilosr2m of the resin.
Production ~a~ple 2 A mixtu-e of 116 parts of 2-hydroxyethyl acrylate, * Trade mark ,.,; ~
284 parts of glycidyl methacrylate, 600 parts of n-butyl methacrylate and 30 parts of azobisisobutyronitrile was added to a four-necked flask containing 667 parts of n-butyl alcohol at 130C over 3 hours to thereby effect the polymerization reaction. The flask contents were then cooled to 110C, 86 parts of methacrylic acid, 0.5 part of hydroquinone and 1 part of tetra-ethylammonium chloride were further added, and the reaction was allowed to proceed until the acid value became 0 (zero). The reaction mixture was cooled to 70C, then 60 parts of acetic acid and 89 parts of dimethylaminoethanol were further added, and the reaction was allowed to proceed for 5 hours. The thus-obtained resin solution [hereinafter referred to as "resin solution (A-2)"] had a nonvolatile matter content of 65~ and a Gardner viscosity (25C) of P.
The resin obtained had a peak molecular weight of about 12,000 as measured by GPC, and was 0.85 moles in a polymerizable unsaturated group content and 0.85 moles in an onium-containing group content, per kilogram of the resin.
Production Example 3-A carboxyl-terminated polyester having 2 peak molecular weight of about 2,000 as measured by GPC was 25synthesized by dehydration condensation at 220C of 650 - 23 ~ l 3 3 8 5 7 5 parts of itaconic acid and 248 parts of ethylene glycol.
After cooling to 110C, 93 parLs of epichlorohydrin and 727 parts of isobutanol were added to the polyester, and the mixture was heated at 110C until the acid value became 0. To the reaction mixture was further added 90 parts of pyridine, and the resultant mixture was heated at 110C for 15 hours. To the thus-obtained resin solution was added 1,000 parts of water. The chloride ion was eliminated from the resultant mixture by treatment on an anion exchange resin. The so-treat-ed solution was supplemented with 50 parts of 88%
formic acid. The aqueous resin emulsion thus obtained [hereinafter referred to as "resin solution (A-3)"] had a nonvolatile matter content of 35~ and a Gardner viscosity (25C) of B. The resin was 5.3 moles in a polymerizable unsaturated group content and 1.1 moles in an onium-containing group content, per kilogram of the resin.
Comparative Production Example 1 The procedure of Production Example 2 was followed except that 35 parts of sodium ethoxide was used in lieu of 60 parts of acetic acid and 89 parts of dimethylaminoethanol which were used in Production Example 2. Thus was obtained a resin solution [hereinafter referred to as "resin solution (A-4)"].
-- 24 - l 338575 The resin was 0.85 moles in a polymerizable unsaturated group content per kilogram of the resin.
Production of resins (a) having polymerizable unsaturated group Production Example 4 A four-necked flask was charged with a mixture of 627 parts of Epikote No. 154 (Shell Chemical Co.), 883 parts of ethylene glycol monobutyl ether, 252 parts of acrylic acid, 1 part of hydroquinone and 3 parts of tetraethylammonium bromide, and when the contents were heated at 120C for 6 hours, the acid value amounted to not more than 3 and the reaction procedure was terminat-ed. The resin solution obtained [hereinafter referred to as "resin solution (Ba-1)"] had a nonvolatile matter content of 49.5~ and a Gardner viscosity (25C) of K.
The resin had a peak molecular weight of about 900 as measured by GPC, and was 4.0 moles in a polymerizable unsaturated group content per kilogram of the resin.
Production Example 5 Polymerization was carried out by pouring a mixture of 116 parts of 2-hydroxyethyl acrylate, 284 parts of glycidyl methacrylate, 600 parts of n-butyl methacrylate and 30 parts of azobisisobutyronitrile into a four-necked flask containing 1,000 parts of n-butyl alcohol maintained at 130C over 3 hours. The polymerization mixture was cooled to 110C, then supplemented with 172 parts of methacrylic acid, 1 part of hydroquinone and 2 parts of tetraethylammonium chlo-ride, and the resultant mixture was heated at 110C
until the acid value reached 3 or less. The thus-obtained resin solution [hereinafter referred to as "resin solution (Ba-2)~ had a nonvolatile matter content of 54.0% and a Gardner viscosity (25C) of Q.
The resin had a peak molecular weight of about 10,000 as determined by GPC, and was 1.7 moles in a polymeriz-able unsaturated group content per kilogram of the resin.
Production Example 6 A carboxyl-terminated polyester was synthesized by dehydration condensation at 220C of 650 parts of itaconic acid and 248 parts of ethylene glycol, followed by addition of 754 parts of toluene. The resin solution obtained [hereinafter referred to as "resin solution (Ba-3)"] had a nonvolatile matter content of 50.0% and a Gardner viscosity (25C) of Y.
The resin had a peak molecular weight of about 700 as determined by GPC, and was 6.6 moles in a polymerizable unsaturated group content per kllogram of the resin.
Production of resins (b) having onium-containing group P~oduction Example 7 A four-necked flask was charged with a mixture of 627 parts of Epikote No. 154 (Shell Chemical Co.), 1,306 parts of ethylene glycol monobutyl ether, 252 parts of acrylic acid and 427 parts of thiodiglycol, and the mixture was heated at 80C for 3 hours. The resin solution thus obtained [hereinafter referred to as "resin solution (Bb-l)"] had a nonvolatile matter - content of 47.8% and a Gardner viscosity (25C) of P.
The resin had a peak molecular weight of about 1,000 as measured by GPC, and was 2.7 moles in an onium-con-taining content per kilogram of the resin.
Production Example 8 A four-necked flask was charged with a mixture of 900 parts of Epikote No. 1001 (Shell Chemical Co.), 204 parts of pivalic acid, 180 parts of pyridine and 1,284 parts of n-butanol, and the mixture was heated at 50C
for 10 hours. The resin solution obtained [hereinafter referred to as "resin solution (Bh-2)"] had a nonvola-tile matter content of 48.2~ and a Gardner viscosity (25C) of H. The resin had a peak molecular weight of about 1,200 as determined by GPC, and was 1.6 moles in an onium-contai~ing group content per kilogram of the resin.
Production Example 9 A four-necked flask was charged with a mixture of 93 parts of epichlorohydrin, 89 parts of dimethyl-aminoethanol and 50 parts of 88~ formic acid, and the mixture was heated at 70C for 40 minutes. The resin solution thus obtained [hereinafter referred to as "resin solution (Bb-3)"] had a nonvolatile matter content of 95% and a Gardner viscosity (25C) of T.
The resin had a peak molecular weight of about 200 25 measured by GPC, and was 4.4 moles in an onium-contain-ing group content per kilogram of the resin.
Example 1 The resin solution (A-1) obtained above in Production Example 1 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickne,ss and each film was cured by heating at 120C for 10 minutes.
Example 2 The resin solution (A-2) obtained above in Production Example 2 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C for 30 minutes.
Example 3 The resin solution (A-3) obtained above in Production Example 3 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 160C for 5 minutes.
Example 4 A mixture of 98 parts of the resin solution (Ba-l) obtained above in Production Example 4 and 2 parts of the resin solution (Bb-1) obtained above in Production Example 7 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 120C
for 30 minutes.
Example 5 A mixture of 50 parts of the resin solution (Ba-l) obtained above in Production Example 4 and 50 parts of the resin solution (Bb-l) obtained above in Production Example 7 was applied to a polished mild steel plate and a glass plate to a wet film of 100 ~m in thickness and each film was cured by heating at 120C for 30 minutes.
Example 6 A mixture of 30 parts of the resin solution (Ba-1) obtained above in Production Example 4 and 70 parts of the resin solution (Bb-l) obtained above in Production Example 7 was applied to a polished mild steel plate and a glass plate to a wet film of 100 ~m in thickness and each film was cured by heating at 120C for 30 minutes.
Example 7 A mixture of 98 parts of the resin solution (Ba-2) obtained above in Production Example 5 and 2 parts of the resin solution (Bb-2) obtained above in Production Example 8 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C
for 10 minutes.
Example 8 A mixture of 95 parts of the resin solution (Ba-2) obtained above in Production Example 5 and 5 parts of the resin solution (Bb-2) obtained above in Production Example 8 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C
for 10 minutes.
Example 9 A mixture of 70 parts of the resin solution (Ba-2) obtained above in Production Example 5 and 30 parts of the resin solution (Bb-2) obtained above in Production Example 8 was applied to a polished mild steel plate and a glass plate to obtain a wet film of lO0 ~m in 1 33857~
thickness and each film was cured by heating at 100C
for 10 minutes.
Example 10 A mixture of 99.5 parts of the resin solution (Ba-3) obtained above in Production Example 6 and 0.5 part of the resin solution (Bb-3) obtained above in Production Example 9 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 160C for 2 hours.
Example 11 A mixture of 95 parts of the resin solution (Ba-3) obtained above in Production Example 6 and 5 parts of the resin solution (Bb-3) obtained above in Production Example 9 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 160C
for 2 hours.
Example 12 A mixture of 90 parts of the resin solution (Ba-3) obtained above in Production Example 6 and 10 parts of the resin solution (Bb-3) obtained above in Production Example 9 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 160C
for 2 hours.
- 31 - l 33 8 5 ~ 5 Comparative Example 1 The resin solution (A-4) obtained above in Comparative Production Example 1 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C for 30 minutes.
Comparative Example 2 The resin solution (Ba-1) obtained above in Production Example 4 was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 150C for 30 minutes.
Comparative Example 3 A mixture of 98 parts of the resin solution (Ba-1) obtained above in Production Example 4 and 2 parts of benzoyl peroxide was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 150C for 30 minutes.
Comparative Example 4 A mixture of 98 parts of the resin solution (Ba-2) obtained above in Production Example 5 and 2 parts of sodium ethylate was applied to a polished mild steel plate and a glass plate to obtain a wet film of 100 ~m in thickness and each film was cured by heating at 100C for 10 minutes.
Comparative Example 5 A mixture of 95 parts of the resin solution (Ba-3) obtained above in Production Example 3 and 5 parts of tetramethylammonium chloride was applied to a polished mild steel plate and a glass plate to a wet film of 100 ~m in thickness and each film was cured by heating at 160C for 2 hours.
The coated sheets obtained above in Examples 1 to - 12 and Comparative Examples 1 to 5 were tested in the following manner. Thus, the coated glass plates were subjected to acetone extraction test, while the coated mild steel plates were tested for water resistance.
The resin solutions used in Examples 1 to 12 and Comparative Examples 1 to 5 were tested for storage stability. The results thus obtained are shown below in Table 1.
Table 1 Immersion in Water Storage acetone resistance sta~ility Example 1 89.8% Good Good Example 2 96.0% Good Good Example 3 98.8% Good Good Example 4 90.5% Good Good Example 5 98.8% Good Good Example 6 98.5% Good Good Example 7 92.6% Good Good Example 8 94.4% Good Good Example 9 70.4% Good Good Example 10 95.9% Good Good Example 11 95.5% Good Good Example 12 91.0% Good Good Comparative 90.2% Blistering Gelation Example 1 Comparative 0% Whitening & Good Example 2 blistering Comparative 94 0% Good Gelation Example 3 Example 4 88.6% Whitening & Gelation Comparative 85.5% Blistering Good Example 5 Immersion in acetone: Unextracted film proportion after 8 hours of immersion at 40C.
ater resistance : Immersion in deionized water ~40C, 7 days).
torage stability : 40C, 3 months.
Claims (7)
1. A resin composition which is heat-curable on crosslinking, the composition comprising a curable resin containing 0.1 to 10 moles of polymerizable unsaturated group, per kilogram of the resin and 0.01 to 5 moles, per kilogram of the resin, of aprotic onium-containing group of the formula -CH-CH2-W+ -O- COR1 ¦ (I) OH
wherein R1 means a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms which may be substituted by a hydroxyl group, an alkoxy group of 1 to 6 carbon atoms, an ester group of 1 to 6 carbon atoms or a halogen atom; -W+ means wherein Z means a nitrogen atom or phosphorus atom and Y means a sulfur atom; R2, R3 and R4 are the same or different and respectively mean an organic group of 1 to 14 carbon atoms, and R2 and R3, or R2, R3 and R4 may jointly form a heterocyclic group taken together with the adjacent nitrogen, phosphorus or sulfur atom, wherein said resin is of an acrylic, polyester, urethane, alkyd, epoxy or phenolic type, and has a peak molecular weight of about 250 to about 100,000 as determined by gel permeation chromatography, the resin composition being cured by heating at a temperature not lower than 80°C for a period of not shorter than 5 minutes.
wherein R1 means a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms which may be substituted by a hydroxyl group, an alkoxy group of 1 to 6 carbon atoms, an ester group of 1 to 6 carbon atoms or a halogen atom; -W+ means wherein Z means a nitrogen atom or phosphorus atom and Y means a sulfur atom; R2, R3 and R4 are the same or different and respectively mean an organic group of 1 to 14 carbon atoms, and R2 and R3, or R2, R3 and R4 may jointly form a heterocyclic group taken together with the adjacent nitrogen, phosphorus or sulfur atom, wherein said resin is of an acrylic, polyester, urethane, alkyd, epoxy or phenolic type, and has a peak molecular weight of about 250 to about 100,000 as determined by gel permeation chromatography, the resin composition being cured by heating at a temperature not lower than 80°C for a period of not shorter than 5 minutes.
2. A composition as claimed in Claim 1, wherein said resin has at least one polymerizable unsaturated group per molecule.
3. A composition as claimed in Claim 1, wherein the polymerizable unsaturated group is at least one selected from the group consisting of acryloyl, methacryloyl, itaconoyl, maleoyl, fumaroyl, crotonoyl, acrylamido, methacrylamido, cinnamoyl, vinyl and allyl groups.
4. A resin composition which is heat-curable on crosslinking, the composition comprising (a) a resin having 0.1 to 10 moles of polymerizable unsaturated group, per kilogram of the resin (a), and (b) a resin having 0.01 to 5 moles, per kilogram of the resin (b), of aprotic onium-containing group of the formula (I) shown in Claim 1, wherein each of said resins (a) and (b) is of an acrylic, polyester, urethane, alkyd, epoxy or phenolic type, and said resin (a) has a peak molecular weight of about 250 to about 100,000 as determined by gel permeation chromatography, and said resin (b) has a peak molecular weight of about 150 to about 100,000 as determined by gel permeation chromatography, the resin composition being cured by heating at a temperature not lower than 80°C for a period of not shorter than 5 minutes.
5. A composition as claimed in Claim 4, wherein the resin (a) is a resin containing hydroxyl group.
6. A composition as claimed in Claim 4, wherein said resin has at least one polymerizable unsaturated group per molecule.
7. A composition as claimed in Claim 4, wherein the polymerizable unsaturated group is at least one selected from the group consisting of acryloyl, methacryloyl, itaconoyl, maleoyl, fumaroyl, crotonoyl, acrylamido, methacrylamido, cinnamoyl, vinyl and allyl groups.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62311653A JP2609881B2 (en) | 1987-12-08 | 1987-12-08 | Curable resin composition and curing method thereof |
| JP311653 | 1987-12-08 | ||
| JP311652 | 1987-12-08 | ||
| JP31165287A JP2612457B2 (en) | 1987-12-08 | 1987-12-08 | Curable resin and its curing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1338575C true CA1338575C (en) | 1996-09-03 |
Family
ID=26566842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000584748A Expired - Fee Related CA1338575C (en) | 1987-12-08 | 1988-12-01 | Curable resin composition |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR910008608B1 (en) |
| CA (1) | CA1338575C (en) |
| DE (1) | DE3841413A1 (en) |
| GB (1) | GB2213488B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3914407A1 (en) * | 1989-04-29 | 1990-10-31 | Basf Ag | RADIATION-SENSITIVE POLYMERS AND POSITIVE WORKING RECORDING MATERIAL |
| JPH07114183A (en) * | 1993-10-15 | 1995-05-02 | Sony Corp | Photopolymerizable composition and formation of cured coating film pattern using the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4338232A (en) * | 1977-12-27 | 1982-07-06 | The Dow Chemical Company | Radiation-curable resins |
| US4857566A (en) * | 1987-04-21 | 1989-08-15 | The Dow Chemical Company | Curable latex composition, films and foams formed therefrom and method for curing the composition |
-
1988
- 1988-12-01 CA CA000584748A patent/CA1338575C/en not_active Expired - Fee Related
- 1988-12-02 GB GB8828256A patent/GB2213488B/en not_active Expired - Fee Related
- 1988-12-08 DE DE3841413A patent/DE3841413A1/en active Granted
- 1988-12-08 KR KR1019880016354A patent/KR910008608B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR910008608B1 (en) | 1991-10-19 |
| GB2213488B (en) | 1991-11-27 |
| GB8828256D0 (en) | 1989-01-05 |
| KR890010089A (en) | 1989-08-05 |
| GB2213488A (en) | 1989-08-16 |
| DE3841413C2 (en) | 1992-04-30 |
| DE3841413A1 (en) | 1989-06-22 |
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