CA1112788A - Crosslinking aqueous coating agents - Google Patents
Crosslinking aqueous coating agentsInfo
- Publication number
- CA1112788A CA1112788A CA295,557A CA295557A CA1112788A CA 1112788 A CA1112788 A CA 1112788A CA 295557 A CA295557 A CA 295557A CA 1112788 A CA1112788 A CA 1112788A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- aqueous coating
- oil
- alkyd resin
- 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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/16—Esters of inorganic acids
- C09D101/18—Cellulose nitrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
-
- 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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Aqueous coating agent consisting of 5 - 50 parts by weight of cellulose ester, 5 - 30 parts by weight of plasticiser, 5 - 50 parts by weight of alkyd resin, 30 - 80 parts by weight of water and 0.1 - 10 parts by weight of emulsifier, wherein the emulsifier is a vinyl alcohol homopolymer or copolymer and the alkyd resin is a short-oil alkyd resin having 5 - 50 % by weight of oil, characterised in that it additionally contains 4 - 40 parts by weight of a urea resin and/or melamine resin.
Aqueous coating agent consisting of 5 - 50 parts by weight of cellulose ester, 5 - 30 parts by weight of plasticiser, 5 - 50 parts by weight of alkyd resin, 30 - 80 parts by weight of water and 0.1 - 10 parts by weight of emulsifier, wherein the emulsifier is a vinyl alcohol homopolymer or copolymer and the alkyd resin is a short-oil alkyd resin having 5 - 50 % by weight of oil, characterised in that it additionally contains 4 - 40 parts by weight of a urea resin and/or melamine resin.
Description
Aqueous coating agents, ~or example for lacquering furniture, have hi-therto generally contained syn-thetic resins, such as acrylic polymers or cellulose esters, as -the film-forming agents. Methods for preparing aqueous emulsions of suitable cellulose derivatives are known and are described, ~or example9 in German Auslegeschrift (German Published Specific.) 1,286,672 and U,S. Patent Specification 3,615,792, Emul-sions of cellulose esters, for example of nitrocellulose, cannot be used as the sole binders for coating agents9because they only produce brittle and fragile ~ilms. They must be com-bined with ketone resins or vinyl acetate copolymers in order to achieve glossy coatings with good mechanical properties.
Cellulose esters, for example nitrocellulose, mostly combined with alkyd resins, are used for lacquering wood or similar materials. This combination leads to coatings o~
high gloss 7 adequate hardness, good elasticity and excellent pore ~low, but it is not possible -to work with aqueous emul-sions; instead, these combinations have hitherto had to be processed from organic solutions~ All attempts hitherto to emulsify alkyd resins and cellulose e$ters lead either to emulsions of inadequate stability or to emulsions with particles which are too coarse and which do not permit levelling to give ~3C~ glossy ooatirigs O~r cope~ding~Application (Specification Serial No. P'~7 03 075~i~) relates to aquçous dispersions o~ coating agents, consisting o~ 5 - 50 parts by weight of cellulose ester, 5 - 30 parts by weight of plasticisert 5 - 50 parts by weight of alkyd resin, 30 - 80 parts by weight of water and 0~5 - 10 parts by weight o~
:
emulsifier~ which contain a vinyl alcohol hom~polymer or copolymer clS the emulsi~ier and a short-oil alkyd resin9 containing 5 - 50% by weight of oil, as the al~yd resin.
: . : ' ' . -7~1 These dispersion~ are stable and give coating~ of acceptable gloss.
The a~ore-mentioned copending applica-tion furth~r rela-tes to a process for -the prep2ration of such dispersions of soatin~
agents, in which a cellulose ester, an alkyd resin and a plastic-iser are dissolved in an organic solven-t, this solution is dispers-ed into a solution consisting of emulsi~ier and water and th~
organic solvent ls removecl k~y distillation. According to the present inventionS there is provide(l an aqueous coating agent consisting of 5 to 50 parts by weight o~ cellulose ester, 5 -to 30 parts by weight of plastiGiser, 5 to 50 parts by weight of alkyd resin, 30 to 80 parts by ~ieight of water, 0.1 to 10 parts by weight of emulsifier, wherein the emulsi~ier is a vinyl alcohol homopolymer or copolymer and the alkyd resin is a short-oil alkyd resin having 5 to 50 % by weight o~ oil, and 4 to 40 parts by weight of a urea resin and/or melamine resin (as hereinbefore defined).
The size of the dispersed particles is particularly important for -the stability o~ the dispersion and also ~or its behaviaur in film formation According to -the in~ention it is preferably O.l to 0.5 ~ and it does not change substantially even on prolonged storage at 5 - 50C, Cellulose esters which can be used according to the invention are9 in particular, cellulose acetate, cellulose acetobutyrate, cellulose acetate-benzoate and cellulose sorbate acetate and mixtures of these esters, Nitrocellulose, ~or example the customary collodion cotton grades, that is ~o say cellulose nitric acid esters having a nitrogen content o~
10.2 to l2.4% by wel~ht, is very particularly suitable.
Plasticisers in the sense o~ the invention are, in particular, esters, such as dlbutyl phthalate, dioctyl Le A 17 838 ~- 3 -- . : -. .
.
, phthalate, dicyclohexyl phthalate, dibutyl adipate, benzyl butyl adipate, dioctyl adipate, phosphoric acid esters, such as tricresyl phosphate, tri-phenyl phosphate or trioctyl phosphate, and also benzenesulphonic acid N-methylamide.
Suitable alkyd resins are preferably oil-modified or fatty acid-modified alkyd resins. Alkyd resins are understood as polyesters which are prepared from alcohols and carboxylic acids by polycondensation according to known processes and such as are defined, for example, in Ullmanns Enzyklo-padie der Technischen Chemie (Ullmann's Encyclopaedia o~ Tndustrial Chemistry) 10 or are described in D.ll. Solomon, The Chemistry Oe Organic Filmformers, page75-101. In general, the alcohols employed contain 1 to 15, preferably 2 to 6, C atoms and the acids used, or their ester-forming derivatives, contain 2 to 14, preferably 4 to 12, C atoms. These alkyd resins can optionally be mixed with other polyesters, for example also with oil-free polyesters.
Examples of suitable alcohols are pentaerythritol, glycerol, tri-methylolpropane, trimethylolethane, 1,2,4-butane-triol, 1,2,6-hexanetriol, ethylene glycol, propane-1,2-dioI, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol and butane-1,4-diol, neopentyl glycol, diethylene glycol, trithylene glycol, dipropylene glycol, hexane-1,6-diol, 1,2-bis-~hydroxy-methyl)-cyclo-20 hexane and 1,4-bis-~hydroxymethyl)-cyclohexane, 2-ethylpropane-1,3-diol, 2-ethylhexane-1,3-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol and adipic acid bis-~ethylene glycol~ ester; benzyl alcohol, cyclohexanol and other mono-alcohols with 1 to 6 C atoms. Preferred alcohols are glycerol, trimethylol-propane, neopentyl glycol and pentaerythritol.
The follolaing carboxylic acids, or their ester-forming derivatives, ma~ be mentioned as examples of suitable acid ~ . . , . : ,.
.
.~D~O ~
componen-ts: ph-thalic acid, isophthalic acid, terephthalic acid, -te-trahydrophthalic acid c~d hexahydroph-thalic acid, endo-methylenete-trahydrophthalic acid, succinic acid, adipic acid, sebacic acid, trimellitic acid, benzoic acid and -their derivatives 9 such as, for example, p~tert.-butylbenzoic acid and hexahydrobenzoic acid. Phthalic acid is the most customary.
In the alkyd resins which are employed for the coating emulsions according to the i~vention, the proportion o~ oil can be 5 to 50% by weight, calculated as triglyceride and relative to the alkyd resin. The drying or non-drying fat-ty acids, which generally contain 6 to 24 C atoms, can be employed either as such or in the form of their glycerol es-ters (tri-glycerides). Animal and vegetable oils, fats or fatty acids, such as, ~or example 9 coconut oil, groundnu-t oil, castor oil, olive oil, soya bean oil ? linseed oil, cottonseed oil~
sa~floweroil orthe correspondingfatty acid~ dehydrated castor oil or castor oil ~atty acid, mono-unsaturated fatty acids, lard 7 tallow and train oils, tall oil fatty acid and synthetic fatty acids, may be mentioned as being suitable.
Suitable emulsifiers are homopolymers and copolymers of vinyl alcoholl for example polyvinyl alcohols which are formed by hydrolysis of polyvinyl acetate and which are available i commercially, for example under the designation Polyviol W
25/240 and W 25/140~ Hydrolysed copolymers of vinyl-pyrrolidone and vinyl acetate are also suitable.
The dispersions of coating agents of the invention preferably contain alkyd resins with an oil content of 20 to 45% by weight.
The coating agents according to the invention can be prepared by dissolving the alkyd resin, the cellulose ester and the plasticiser in a polar solvent which ls not soluble in water, and which can be removed by distillation from the emulsion to ~ 5 ~
Tr~
. .
~L~$~
be formed, combining the solution with an aqueous solution of the emulsifier and thus forming an oil-in-water emulsion by means of high shearing forces. The organic solvent is then removed, on its own or in the form o~ an aqueous azeotrope, by distillation. Solven-ts which are particularly suitable are alkyl acetate and alkyl propionate. The aqueous emulsion which remains can be dilu-ted with more water or a suitable coalescing agent can be added to it. In the following tex-t this will be designated a secondary emulsion.
One or more coalescing or aggregating agents can also be added to the dispersion in order to achieve a clear film of high gloss. Coalescing agents which form an azeotrope with the water are preferred here. It is then necessary to add to the dispersion sufficient coalescing agent so that the azeotrope is first distilled off and, in addition, to add further coalescing agent which effects the aggregation of the particles Possible coalescing agents are ethylene glycol monomethyl ether, ethylene glyool monoethyl ether and ethylene glycol monobutyl ether-acetate, diethylene glycol, diethylene glycol monobutyl ether, diacetone alcoho~ methylglycol acetate, methyl amyl ketone and diisobutyl ketone.
The primary emulsion consisting of cellulose ester, alkyd resin, emulsifier, plasticiser, water and organic solvent is produced in a commercially available device having an adequately high peripheral speed of 5 to 50 m/second, pre~er-ably 10 - 30 m/second.
Examples are: Ultra-Tu ~ type 45 of 10,000 re~olutions per minute; Gaulin~Homogeniser? Dissolver and bead mills.
The emulsifying time in theUltra-Tu~ axshould not be more than 2 minute$, since otherwise too great an evolution of~
heat takes place. This tlme is ade~uate to produce small, spherical partlcles of 0.1 - 0.5 ~ from the constituents of the ultimate emulsion.
~ ~ - 6 -:
, ' ' ' . - ~
~ ~,t~ 3 In the sense o~ -the invention, urea resins and mela-mine resins are condensation produc-ts o~, respec-tively, urea or melaminewith ~o~aldehydewhich havebeenpreparedin analkaline medium. These productsare knownfrom theliterature, They are generally water-soluble and are added in the form of aqueous solutions to -the dispersions ofour a~ore-mentioned copending application. They cause cro3slinking of the coatings prepared from the dispersions and thus improve the stability and gloss v~
the coatings. Catalytic amounts of p-toluenesulphonic acid can be added in order to accelera-te the crosslinking.
Example 1 (Comparison) A lacquer of the following composition was prepared:
groundnut oil ~atty acid alkyd resin having 41% of oil, 60% strength solution in xylene152 parts by weight collodion cotton (cellulose nitric acid ester containing approximately 12% o~
nitrogen), Standard Specification type 24 E, DIN 53~1799 in the form of chips111 parts by weight dibutyl phthalate 8 parts by weight ethylene glycol monoethyl ether59 parts by weight butyl acetate 190 parts by weight ethyl acetate 140 parts by weight xylene 300 parts by weight ethylglycol acetate40 parts by weight The resulting lacquer exhibited a viscosity correspond-ing to a flow time of approximately 30 seconds~ measured in accordance with DIN 5~211 (DIN cup No. 4~. The curing to give ~ilms and the assessment are described in Table 1.
; 30 Example 2 A lacquer of the following composition was prepared:
~ Le A 17 8~ - 7 _ :: :
-, . - , .
- . . .
dispersion -From Example 1 oF Canadian application Serial No. 295,556 as described on page 2 of the present application, ~0% strength in water 580 parts by weight ethylene glycol monoethyl ether3~ parts by weight ethylglycol acetate 34 parts by weight ethylene glycol monomethyl ether3~ parts by weight methylglycol acetate 3~ parts by weight ~-me-thyl-~-hydroxy-pentan-2-one3~ parts by weight Resimene 980X1 70 parts by weight water 17~ parts by weight levelling agent (alkylbenzenesulphonate) 6 parts by weight 1,000 parts by weight para-toluenesulphonic acid, 25%
strength solution in water17 parts by weight 1) methylated, non-plasticised water-soluble urea resin from Messrs. Monsanto. Trade mark.
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CH ~ h .~ r l O 1 +' a) o t~tH ~ S~ h (D U~
h U) !~ tdl h tH ~, ~ j CO c~O
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Cellulose esters, for example nitrocellulose, mostly combined with alkyd resins, are used for lacquering wood or similar materials. This combination leads to coatings o~
high gloss 7 adequate hardness, good elasticity and excellent pore ~low, but it is not possible -to work with aqueous emul-sions; instead, these combinations have hitherto had to be processed from organic solutions~ All attempts hitherto to emulsify alkyd resins and cellulose e$ters lead either to emulsions of inadequate stability or to emulsions with particles which are too coarse and which do not permit levelling to give ~3C~ glossy ooatirigs O~r cope~ding~Application (Specification Serial No. P'~7 03 075~i~) relates to aquçous dispersions o~ coating agents, consisting o~ 5 - 50 parts by weight of cellulose ester, 5 - 30 parts by weight of plasticisert 5 - 50 parts by weight of alkyd resin, 30 - 80 parts by weight of water and 0~5 - 10 parts by weight o~
:
emulsifier~ which contain a vinyl alcohol hom~polymer or copolymer clS the emulsi~ier and a short-oil alkyd resin9 containing 5 - 50% by weight of oil, as the al~yd resin.
: . : ' ' . -7~1 These dispersion~ are stable and give coating~ of acceptable gloss.
The a~ore-mentioned copending applica-tion furth~r rela-tes to a process for -the prep2ration of such dispersions of soatin~
agents, in which a cellulose ester, an alkyd resin and a plastic-iser are dissolved in an organic solven-t, this solution is dispers-ed into a solution consisting of emulsi~ier and water and th~
organic solvent ls removecl k~y distillation. According to the present inventionS there is provide(l an aqueous coating agent consisting of 5 to 50 parts by weight o~ cellulose ester, 5 -to 30 parts by weight of plastiGiser, 5 to 50 parts by weight of alkyd resin, 30 to 80 parts by ~ieight of water, 0.1 to 10 parts by weight of emulsifier, wherein the emulsi~ier is a vinyl alcohol homopolymer or copolymer and the alkyd resin is a short-oil alkyd resin having 5 to 50 % by weight o~ oil, and 4 to 40 parts by weight of a urea resin and/or melamine resin (as hereinbefore defined).
The size of the dispersed particles is particularly important for -the stability o~ the dispersion and also ~or its behaviaur in film formation According to -the in~ention it is preferably O.l to 0.5 ~ and it does not change substantially even on prolonged storage at 5 - 50C, Cellulose esters which can be used according to the invention are9 in particular, cellulose acetate, cellulose acetobutyrate, cellulose acetate-benzoate and cellulose sorbate acetate and mixtures of these esters, Nitrocellulose, ~or example the customary collodion cotton grades, that is ~o say cellulose nitric acid esters having a nitrogen content o~
10.2 to l2.4% by wel~ht, is very particularly suitable.
Plasticisers in the sense o~ the invention are, in particular, esters, such as dlbutyl phthalate, dioctyl Le A 17 838 ~- 3 -- . : -. .
.
, phthalate, dicyclohexyl phthalate, dibutyl adipate, benzyl butyl adipate, dioctyl adipate, phosphoric acid esters, such as tricresyl phosphate, tri-phenyl phosphate or trioctyl phosphate, and also benzenesulphonic acid N-methylamide.
Suitable alkyd resins are preferably oil-modified or fatty acid-modified alkyd resins. Alkyd resins are understood as polyesters which are prepared from alcohols and carboxylic acids by polycondensation according to known processes and such as are defined, for example, in Ullmanns Enzyklo-padie der Technischen Chemie (Ullmann's Encyclopaedia o~ Tndustrial Chemistry) 10 or are described in D.ll. Solomon, The Chemistry Oe Organic Filmformers, page75-101. In general, the alcohols employed contain 1 to 15, preferably 2 to 6, C atoms and the acids used, or their ester-forming derivatives, contain 2 to 14, preferably 4 to 12, C atoms. These alkyd resins can optionally be mixed with other polyesters, for example also with oil-free polyesters.
Examples of suitable alcohols are pentaerythritol, glycerol, tri-methylolpropane, trimethylolethane, 1,2,4-butane-triol, 1,2,6-hexanetriol, ethylene glycol, propane-1,2-dioI, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol and butane-1,4-diol, neopentyl glycol, diethylene glycol, trithylene glycol, dipropylene glycol, hexane-1,6-diol, 1,2-bis-~hydroxy-methyl)-cyclo-20 hexane and 1,4-bis-~hydroxymethyl)-cyclohexane, 2-ethylpropane-1,3-diol, 2-ethylhexane-1,3-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol and adipic acid bis-~ethylene glycol~ ester; benzyl alcohol, cyclohexanol and other mono-alcohols with 1 to 6 C atoms. Preferred alcohols are glycerol, trimethylol-propane, neopentyl glycol and pentaerythritol.
The follolaing carboxylic acids, or their ester-forming derivatives, ma~ be mentioned as examples of suitable acid ~ . . , . : ,.
.
.~D~O ~
componen-ts: ph-thalic acid, isophthalic acid, terephthalic acid, -te-trahydrophthalic acid c~d hexahydroph-thalic acid, endo-methylenete-trahydrophthalic acid, succinic acid, adipic acid, sebacic acid, trimellitic acid, benzoic acid and -their derivatives 9 such as, for example, p~tert.-butylbenzoic acid and hexahydrobenzoic acid. Phthalic acid is the most customary.
In the alkyd resins which are employed for the coating emulsions according to the i~vention, the proportion o~ oil can be 5 to 50% by weight, calculated as triglyceride and relative to the alkyd resin. The drying or non-drying fat-ty acids, which generally contain 6 to 24 C atoms, can be employed either as such or in the form of their glycerol es-ters (tri-glycerides). Animal and vegetable oils, fats or fatty acids, such as, ~or example 9 coconut oil, groundnu-t oil, castor oil, olive oil, soya bean oil ? linseed oil, cottonseed oil~
sa~floweroil orthe correspondingfatty acid~ dehydrated castor oil or castor oil ~atty acid, mono-unsaturated fatty acids, lard 7 tallow and train oils, tall oil fatty acid and synthetic fatty acids, may be mentioned as being suitable.
Suitable emulsifiers are homopolymers and copolymers of vinyl alcoholl for example polyvinyl alcohols which are formed by hydrolysis of polyvinyl acetate and which are available i commercially, for example under the designation Polyviol W
25/240 and W 25/140~ Hydrolysed copolymers of vinyl-pyrrolidone and vinyl acetate are also suitable.
The dispersions of coating agents of the invention preferably contain alkyd resins with an oil content of 20 to 45% by weight.
The coating agents according to the invention can be prepared by dissolving the alkyd resin, the cellulose ester and the plasticiser in a polar solvent which ls not soluble in water, and which can be removed by distillation from the emulsion to ~ 5 ~
Tr~
. .
~L~$~
be formed, combining the solution with an aqueous solution of the emulsifier and thus forming an oil-in-water emulsion by means of high shearing forces. The organic solvent is then removed, on its own or in the form o~ an aqueous azeotrope, by distillation. Solven-ts which are particularly suitable are alkyl acetate and alkyl propionate. The aqueous emulsion which remains can be dilu-ted with more water or a suitable coalescing agent can be added to it. In the following tex-t this will be designated a secondary emulsion.
One or more coalescing or aggregating agents can also be added to the dispersion in order to achieve a clear film of high gloss. Coalescing agents which form an azeotrope with the water are preferred here. It is then necessary to add to the dispersion sufficient coalescing agent so that the azeotrope is first distilled off and, in addition, to add further coalescing agent which effects the aggregation of the particles Possible coalescing agents are ethylene glycol monomethyl ether, ethylene glyool monoethyl ether and ethylene glycol monobutyl ether-acetate, diethylene glycol, diethylene glycol monobutyl ether, diacetone alcoho~ methylglycol acetate, methyl amyl ketone and diisobutyl ketone.
The primary emulsion consisting of cellulose ester, alkyd resin, emulsifier, plasticiser, water and organic solvent is produced in a commercially available device having an adequately high peripheral speed of 5 to 50 m/second, pre~er-ably 10 - 30 m/second.
Examples are: Ultra-Tu ~ type 45 of 10,000 re~olutions per minute; Gaulin~Homogeniser? Dissolver and bead mills.
The emulsifying time in theUltra-Tu~ axshould not be more than 2 minute$, since otherwise too great an evolution of~
heat takes place. This tlme is ade~uate to produce small, spherical partlcles of 0.1 - 0.5 ~ from the constituents of the ultimate emulsion.
~ ~ - 6 -:
, ' ' ' . - ~
~ ~,t~ 3 In the sense o~ -the invention, urea resins and mela-mine resins are condensation produc-ts o~, respec-tively, urea or melaminewith ~o~aldehydewhich havebeenpreparedin analkaline medium. These productsare knownfrom theliterature, They are generally water-soluble and are added in the form of aqueous solutions to -the dispersions ofour a~ore-mentioned copending application. They cause cro3slinking of the coatings prepared from the dispersions and thus improve the stability and gloss v~
the coatings. Catalytic amounts of p-toluenesulphonic acid can be added in order to accelera-te the crosslinking.
Example 1 (Comparison) A lacquer of the following composition was prepared:
groundnut oil ~atty acid alkyd resin having 41% of oil, 60% strength solution in xylene152 parts by weight collodion cotton (cellulose nitric acid ester containing approximately 12% o~
nitrogen), Standard Specification type 24 E, DIN 53~1799 in the form of chips111 parts by weight dibutyl phthalate 8 parts by weight ethylene glycol monoethyl ether59 parts by weight butyl acetate 190 parts by weight ethyl acetate 140 parts by weight xylene 300 parts by weight ethylglycol acetate40 parts by weight The resulting lacquer exhibited a viscosity correspond-ing to a flow time of approximately 30 seconds~ measured in accordance with DIN 5~211 (DIN cup No. 4~. The curing to give ~ilms and the assessment are described in Table 1.
; 30 Example 2 A lacquer of the following composition was prepared:
~ Le A 17 8~ - 7 _ :: :
-, . - , .
- . . .
dispersion -From Example 1 oF Canadian application Serial No. 295,556 as described on page 2 of the present application, ~0% strength in water 580 parts by weight ethylene glycol monoethyl ether3~ parts by weight ethylglycol acetate 34 parts by weight ethylene glycol monomethyl ether3~ parts by weight methylglycol acetate 3~ parts by weight ~-me-thyl-~-hydroxy-pentan-2-one3~ parts by weight Resimene 980X1 70 parts by weight water 17~ parts by weight levelling agent (alkylbenzenesulphonate) 6 parts by weight 1,000 parts by weight para-toluenesulphonic acid, 25%
strength solution in water17 parts by weight 1) methylated, non-plasticised water-soluble urea resin from Messrs. Monsanto. Trade mark.
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.
.~ .
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous coating agent consisting of 5 -to 50 parts by weight of cellulose ester, 5 to 30 parts by weight of plasticiser, 5 to 50 parts by weight of alkyd resin, 30 to 80 parts by weight of water, 0.1 to 10 parts by weight of emulsifier, wherein the emulsifier is a vinyl alcohol homo-polymer or copolymer and the alkyd resin is a short-oil alkyd resin having 5 to 50% by weight of oil, and 4 to 40 parts by weight of a urea resin and/or melamine resin.
2. An aqueous coating agent according to claim 1, in which the cellulose ester is cellulose acetate, cellulose acetobutyrate, cellulose acetate-benzoate, cellulose sorbate-acetate or a mixture thereof or nitrocellulose.
3. An aqueous coating agent according to claim 1 or 2, in which the plasticiser is dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dibutyl adipate, benzyl butyl adipate, dioctyl adipate, tricresyl phosphate, triphenyl phosphate or trioctyl phosphate or benzenesulphonic acid N-methylamide.
4. An aqueous coating agent according to claim 1 or 2, in which the alkyd resin has an oil content of 20 to 45% by weight.
5. An aqueous coating agent according to claim 1 or 2, in which the plasticiser is dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dibutyl adipate, benzyl butyl adipate, dioctyl adipate, tricresyl phosphate, triphenyl phosphate or trioctyl phosphate or benzenesulphonic acid N-methylamide, and in which -the alkyd resin has an oil content of 20 to 45% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2702986.3 | 1977-01-26 | ||
| DE19772702986 DE2702986A1 (en) | 1977-01-26 | 1977-01-26 | CROSS-LINKING AQUATIC COATING AGENTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1112788A true CA1112788A (en) | 1981-11-17 |
Family
ID=5999487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA295,557A Expired CA1112788A (en) | 1977-01-26 | 1978-01-24 | Crosslinking aqueous coating agents |
Country Status (8)
| Country | Link |
|---|---|
| BE (1) | BE863303A (en) |
| CA (1) | CA1112788A (en) |
| DE (1) | DE2702986A1 (en) |
| ES (1) | ES466333A2 (en) |
| FR (1) | FR2378831A1 (en) |
| IT (1) | IT1102805B (en) |
| NL (1) | NL7800512A (en) |
| SE (1) | SE447577B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3111478A1 (en) * | 1981-03-24 | 1982-10-07 | Herberts Gmbh, 5600 Wuppertal | MOTOR VEHICLE WITH MULTI-LAYER PAINTING AND METHOD FOR MULTI-LAYER PAINTING |
| US4551492A (en) * | 1984-12-27 | 1985-11-05 | E. I. Du Pont De Nemours And Company | Polyester coating composition |
| DE3932375A1 (en) * | 1989-09-28 | 1990-10-11 | Henkel Kgaa | Aq. alkyd resin dispersions - used as binder in acid curing lacquers contg. amino resins |
| US5334638A (en) * | 1992-01-21 | 1994-08-02 | Eastman Chemical Company | Aqueous dispersion useful in coatings containing hydrolyzed cellulose ester and acyrlic resin |
| CN105017865A (en) * | 2015-07-29 | 2015-11-04 | 广西梧州龙鱼漆业有限公司 | Wear-resistant wood finish paint |
-
1977
- 1977-01-26 DE DE19772702986 patent/DE2702986A1/en not_active Withdrawn
-
1978
- 1978-01-16 NL NL7800512A patent/NL7800512A/en not_active Application Discontinuation
- 1978-01-24 CA CA295,557A patent/CA1112788A/en not_active Expired
- 1978-01-24 IT IT47760/78A patent/IT1102805B/en active
- 1978-01-25 ES ES466333A patent/ES466333A2/en not_active Expired
- 1978-01-25 BE BE184626A patent/BE863303A/en not_active IP Right Cessation
- 1978-01-25 SE SE7800915A patent/SE447577B/en not_active IP Right Cessation
- 1978-01-26 FR FR7802221A patent/FR2378831A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2702986A1 (en) | 1978-07-27 |
| FR2378831A1 (en) | 1978-08-25 |
| ES466333A2 (en) | 1979-08-01 |
| SE7800915L (en) | 1978-07-27 |
| IT7847760A0 (en) | 1978-01-24 |
| NL7800512A (en) | 1978-07-28 |
| BE863303A (en) | 1978-07-25 |
| IT1102805B (en) | 1985-10-07 |
| FR2378831B1 (en) | 1982-11-19 |
| SE447577B (en) | 1986-11-24 |
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| MKEX | Expiry |