CA2144373A1 - Use of cycloaliphatic diamines for the preparation of plastisols and organosols which are stable in storage - Google Patents
Use of cycloaliphatic diamines for the preparation of plastisols and organosols which are stable in storageInfo
- Publication number
- CA2144373A1 CA2144373A1 CA 2144373 CA2144373A CA2144373A1 CA 2144373 A1 CA2144373 A1 CA 2144373A1 CA 2144373 CA2144373 CA 2144373 CA 2144373 A CA2144373 A CA 2144373A CA 2144373 A1 CA2144373 A1 CA 2144373A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- polymer
- weight
- group
- copolymer
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Cycloaliphatic diamines of the formula
Description
`- 214~373 Use of cvcloaliDhatic ~;r ;n9~ for the DreDaration of Dlastisols and oraanosols which are stable in storaae The present invention relates to the use of specific cycloaliphatic diamines and the products of the reactions thereof with ketones, aldehydes and unsaturated carboxylic acids or carboxylic esters for the preparation of plastisols and organosols which are stable in storage. The invention also relates to plastisols and organosols which are stable in storage and which contain specific cycloaliphatic diamines and the products of the reactions thereof with ketones, aldehydes and unsaturated carboxylic acids or carboxylic esters.
Plastisols and organosols which are stable in storage are known, for example, from EP-A 265 371. The plastisols and organosols described and claimed in the European patent application mentioned, compared with plastisols already known and discussed there as prior art, are distinguished by an improved stability in storage and by the fact that the plastisols and organosols claimed in the European patent application can be gelled at relatively low temperatures. The latter is achieved by the addition of multifunctional, basic substances which can be reacted with the finely divided carboxyl group-containing polymers in the dispersion.
Since plastisols and organosols are playing an increasingly important role in technology, for example, as sealants, as anticorrosive coatings for metals, for the impregnation and coating of substrates made of textiles, for cable insulating, as glues and for the production of composites, the technical demands on the plastisols and organosols,particularly as regards processability and stability in storage, are becoming ever higher.
Le A 30 216-Foreign Countries The object of the present invention is first, to improve in particular the stability in storage of the plastisols and organosols, even at higher ambient temperatures and second, to ensure good gelation at the lowest possible ambient temperatures. The object is fulfilled by using specific cycloaliphatic diamines for the production-of plastisols and organosols.
The invention therefore provides the use of cycloaliphatic diamines of the formula ~ R2 wherein R1, R2, R3, R4, R5 and R6 are identical or different and represent hydrogen or C1-C6 alkyl, preferably C1-C4 alkyl, R7 and R8 are identical or different and represent hydrogen, C1-C6 alkyl, preferably C1-C4 alkyl, or NR1R2 having the me~n;ngS given above for R and R , or represent OR or SR , n represents the numbers 1 to 6, preferably 1 to 4, and also the products of the reactions thereof with ketones, aldehydes and unsaturated or saturated carboxylic acids or carboxylic esters having 2 to 6 C atoms in the acid part and 1 to 4 C atoms in the ester part, Le A 30 216-Foreign Countries 2 . .
optionally in combination with metallic compounds reacting as bases, for the preparation of plastisols and organosols based on organic polymers and organic softeners.
For the preparation of plastisols and organosols, cyclo-aliphatic diamines of the formula R3 ~ R3 Rt ~ CH2 ~ N ~ 2 (II), R R~
wherein Rl to R4 having the me~n;ngs given in formula (I) are preferred, as well as the products of the reactions of the diamines of the formula (II) with ketones, aldehydes and unsaturated or saturated carboxylic acids or carboxylic esters having 2 to 6 carbon atoms in the acid part and 1 to 4 carbon atoms in the ester part.
The use of the following cycloaliphatic diamines is particularly preferred:
4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-diethyldicyclohexylmethane, 2,4,4'-triamino-5-methyldicyclohexylmethane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3,5-diethylcyclohexyl)methane or bis(4-amino-3-methyl-5-ethylcyclohexyl)methane.
Le A 30 216-Foreign Countries 3 ` ``~ 2144373 Besides the above-mentioned products of the reaction of the diamines with ketones, aldehydes and unsaturated or saturated carboxylic acids or carboxylic esters, the corresponding products of the addition of the cyclo-aliphatic diamines and oligomeric compounds to, for example, water, mineral acids (HCl, H2SO4) or glycols (for example, diethylene glycol) can also be used. The reaction of the cycloaliphatic diamines according to the invention with ketones, aldehydes and unsaturated carboxylic acids or carboxylic esters, and the addition of the above-mentioned compounds to the diamines according to the invention are known reactions and are generally described, for example, in Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Organo-Stickstoffverbindungen IV, Part 2, Volume E 16d, pages 646-1329.
The following may be given as examples of ketones, aldehydes, unsaturated carboxylic acids or carboxylic esters which are suitable for the above-mentioned reaction with the diamines according to the invention: isobutyraldehyde, fumaric acid ethyl ester, maleic acid, acetic acid; isobutyraldehyde is preferred. Suitable compounds for addition to the diamines are water, hydrochloric acid, sulphuric acid, preferably water.
The cycloaliphatic diamines according to the invention, the reaction products thereof and the addition products thereof can be used both individually and in mixtures with one another for the preparation of plastisols and organosols.
It is moreover possible to use the cycloaliphatic diamines according to the invention or the reaction products or addition products thereof together with basic metallic compounds for the preparation of plastisols and organosols. In particular zinc oxide, calcium carbonate, magnesium oxide, magnesium carbonate and calcium stearate are suitable basic Le A 30 216-Foreign Countries 4 metallic compounds; zinc oxide and calcium stearate are particularly preferred.
The cycloaliphatic diamines according to the invention and the reaction products and addition products thereof (for brevity referred to below as "diamines according to the invention") can be used in quantities of from 0.1 to 20% by weight, referred to the quantity of polymer. The diamines according to the invention are preferably used in quantities of from 0.5 to 5% by weight.
If basic metallic compounds are used concomitantly in the preparation of plastisols and organosols, these can be used in quantities of from 0.5 to 150% by weight, referred to the quantity of polymer, particularly in quantities of from 1 to 50%
by welght.
Plastisols are in general dispersions of finely divided resins in plasticizers (i.e. softeners). Usually plastisols are in the paste form at normal temperatures and become gels when heated to certain temperatures as a result of solvation of the resin particles by the plasticizers. If volatile solvents are included, the plastisols are called as organosols (see Hawley's Condensed Chemical Dictionary, Twelfth Edition, by Richard J. Lewis, Jr. - Van Nostrand Reinhold Company, New York).
Plastisols and organosols which are particularly suitable for stabilisation by the diamines according to the invention are copolymers, in the form of finely divided particles, of any monomers and polymerisable acids, for example, copolymers of vinyl chloride, vinylidene chloride, acrylates, methacrylates, maleates, styrene, methylstyrene, acrylamides, vinyl esters, methacrylonitrile, vinyl ethers, acrylonitrile, olefins or dienes with polymerisable acids such as, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid. Preferred plastisols are those based on styrene-acrylonitrile (SAN) resins containing a proportion of from 5 to 60% by weight of acrylonitrile, preferably from 5 to 40% by weight, particularly from 10 to 35%
by weight, wherein the SAN resin advantageously still contains a small quantity of acid (from 0.5 to 15% by weight, particularly 2 to 7% by weight). Also preferred are plastisols based on polyvinyl chloride and polymethacrylates as well as the copolymers thereof. Some of them are commercially available, for example, Vestolit E type polyvinyl chloride available from Huls AG of Germany, Plex 4944 polymethyl methacrylate available from Rohm & Haas of U.S.A. and Geon 137 polyvinyl chloride available from Goodrich of U.S.A. which contains approximately 6% of acrylic acid.
Suitable organic plasticizers (softeners) are high-boiling organic solvents which function as softeners at an elevated temperature, such as are already known in the preparation of plastisols and organosols. In this connection reference is made to DE 24 54 235 and EP 265 371. The plasticizer, i.e. the liquid phase, used can be any liquid which brings about the abovementioned gelation at elevated temperatures. It is important for this liquid to have very low volatility, since otherwise the plasticizer could gradually * Trade-mark escape during the storage of the completely gelled plastisols and undesirable changes in their properties could occur.
Commercially important plasticizers are for example the esters of phthalic, adipic, sebacic, phosphoric and citric acid, chlorinated hydrocarbons, liquid polyesters and epoxidised natural oils such as linseed oil or soybean oil. High-boiling polymerizable liquids which are copolymerized during gelation such as multifunctional acrylic or allyl compounds, can also be used as plasticizers. Such plasticizers are for example higher-boiling, predominantly polyfunctional acrylic or allylcompounds. A comprehensive definition of the plasticizer and an explanation of the chemical and physical interactions which occur between a plasticizer and a polymer can be found in:
"Beschichten mit Lacken und Kunststoffen" (Coating with lacquers and plastics), K. Weinmann (Verlag W.A. Colom, Stuttgart, 1967), pages 47 to 158.
A certain quantity of volatile solvents can be added to the plastisols according to the invention to regulate their processing properties. If the content of volatile solvents is about 5 to 10% the plastisols are referred to as organosols (cf.
for example H.A. Sarvertnick, "Plastisols and organosols", page 201, Nostrand Reinhold Company, New York 1972).
The quantity of the plasticizers is usually from 30 to 150 parts by weight, preferably ~rom 80 to 120 parts by weight per 100 parts by weight of the organic polymer used.
6a `- 2144373 The present invention therefore also provides plastisols and organosols based on organic polymers and organic plasticizers, which contain cycloaliphatic diamines of the formula 214~373 ~N ~ R2 wherein R1, R2, R3, R4, R5, R6, R7 and R8 and n have the me~n; ngs previously given, and also the products of the reactions thereof with ketones, aldehydes and unsaturated or saturated carboxylic acids or carboxylic esters having 2 to 6 carbon atoms in the acid part and 1 to 4 carbon atoms in the ester part, and optionally basic metallic compounds.
The plastisols and organosols according to the invention are prepared in a conventional manner by mixing the organic polymers with the organic softeners and the cycloaliphatic diamines according to the invention. The mixing of the paste is carried out in a manner known to the person skilled in the art. The stabilising additives are dissolved or dispersed in the softeners in an appropriate manner. In individual cases it may be advantageous to store the ready-mixed paste for 10 to 48 hours at 5 to 15C prior to further processing.
Besides the diamines mentioned according to the invention, other additives can be added to the plastisols and organosols according to the invention, such as inert fillers, for Le A 30 216-Foreign Countries 7 214437~
example, chalks, heavy spar, kaolin, highly dispersed silica powders, aluminium silicates, talc, glass powder, sand, aluminium oxide and aluminium hydroxide, antimony trioxide, metal soaps, titanium dioxide, carbon black, dyes, pigments and all kinds of surface-treated (e.g. silanised) fillers and pigments, as well as corrosion inhibitors, agents for controlling viscosity, stabilisers against heat, light and oxidation, expanding agents and bonding agents. In this connection, reference is made to DE 24 54 235. Suitable bonding agents are those known to persons skilled in the art, such as for example: one- and two-component isocyanate bonding agents (Desmodur, Desmophen and Desmocap, from Bayer), preferably blocked systems, epoxy bonding agent systems (from Ciba), and polyaminoamides (such as for example the Euretek types from Witco or the Nourybond types from Akzo), resorcinol-cont~;n;ng systems and free-radical polymerisable monomers such as triethylene glycol dimethacrylate.
The bonding agent can be appropriately dispersed in the paste or already applied to the polymer particles during the processing of the latex - during the spray-drying process. If importance is attached to a combination of adhesion and sufficient storability, all the known bonding agents can be used which have a sufficiently low reactivity towards the stabilising additives of formula I to prevent any undesired reaction between the bonding agent component and the stabilising additive. Polyaminoamides and blocked isocyanates are particularly suitable bonding agents for this purpose. Due to the crosslinking reaction of the diamine with for example isocyanates an additional positive effect can be obtained as the mechanical properties, apart from the higher storability.
The additives mentioned can be added to the plastisols and organosols according to the invention in quantities of from Le A 30 216-Foreign Countries 8 ~ 2144373 0.5 to 250% by weight, preferably from 15 to 150% by weight, referred to the polymer used. The optimal quantity can be easily established by appropriate prel;min~ry tests.
The plastisols according to the invention are particularly suitable as sealants, as anticorrosive coatings for metals, coated sheets, for the impregnation and coating of substrates made of textiles or paper, for cable insulating, as glues and for the production of composites.
Le A 30 216-Foreign Countries 9 ` 214~373 Exam~les Exam~le~ lA ~na lB:
A spray-dried emulsion polymer consisting of 59 parts of styrene, 25 parts of acrylonitrile, 10 parts of butyl acrylate and 6 parts of acrylic acid is used to prepare a paste with Unimol~ BB (benzyl butyl phthalate, BayerJ:
lA: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) lB: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 5 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane Both pastes are thinly viscous ;mme~iately after preparation.
After storage at 23C, the sample lA is highly viscous or rubbery after 48 hours, whilst the sample lB remains pasty for at least 90 days. Both samples can be gelled at temperatures of from 130 to 160C to form soft, elastic rubber gels, while the sample supplied with the additive (gelation at 160C) shows distinctly improved mechanical properties.
lA lB
Strength 0.85 3.71 (MPa) (determined according to DIN 53 455) Elongation 660 286 (~) (determined according to DIN 53 455) * Trade-mark `~ 21g4373 ~x~m~le8 2A ~nd 2s A spray-dried emulsion polymer consisting of 64 parts of styrene, 10 parts of acrylonitrile, 20 parts of butyl acrylate and 6 parts of acrylic acid is used to prepare a paste:
2A: 40 g of polymer 60 g of di-2-ethyl hexyl phthalate 2B: 40 g of polymer 60 g of di-2-ethyl hexyl phthalate 2 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane Both the samples were obtained in the form of pastes of low viscosity. The pastes are first of all stored at 8C for 24 h.
This is followed by storage at 45C. While the sample 2A has already gelled after 2 minutes, the sample 2B can be stored for 4 hours without gelling completely. Both samples can be gelled at temperatures of from 130 to 160C to form soft, elastic rubber gels.
Rxam~le~ 3A ~nd 3s A brand of E-PVC (Vestolit E 7012, Huls AG, Germany) was mixed with benzyl butyl phthalate (Unimoll BB) in a dissolver to form a paste of low viscosity:
3A: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 3B: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 2 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane * Trade-mark , 11 .
214~37~
231~9-7749 The test of the storability is carried out in a viscometer at a constant rate of rotation of 400 rev/min and measurements are taken at a temperature of 55C. Whilst the paste 3A
already shows a distinct increase in viscosity after 41 minutes, the sample 3B remains llnchAnged for 5 hours.
Ex~mol~ ~ ~n~ 41~
A PMMA brand of paste from the firm Rahm, Germany (Plex 4944 F) was made into a paste with Unimoll BB, Bayer AG, in a dissolver:
4A: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 4B: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 2 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane Both pastes are doughy immediately after preparation. After storage at 55C, the sample 4A has gelled after 75 minutes, whilst the sample 4B remains pasty to mouldable for at least 3 hours. Both samples can be gelled at temperatures of from 140 to 160C to form soft, elastic rubber gels.
Ex~moleR 5A ~n~ 5~
A spray-dried emulsion polymer consisting of 59 parts of styrene, 25 parts of acrylonitrile, lO parts of butyl acrylate and 6 parts of acrylic acid is used to prepare a paste with MesamoIl*(alkylsulphonic ester, Bayer) as softener:
SA: 40 g of p~lymer 60 g of alkylsulphonic ester (Mesamoll, Bayer) * Trade-mark 214~373 5B: 40 g of polymer 60 g of alkylsulphonic ester (Mesamoll, Bayer) 5 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane Both pastes are thinly viscous immediately after preparation.
After storage at 55C, the sample 5A is highly viscous or rubbery after 150 minutes, whilst the sample 5B r~m~;ns pasty to doughy at 65C for at least 1100 minutes. Both samples can be gelled at temperatures of from 130 to 160C to form soft, elastic rubber gels.
~camDles 6A to 6I.
2000 ml of latex of an emulsion polymer consisting of 25% ACN, 6% acrylic acid, 10% butyl acrylate and 59% styrene was worked up by spray drying. 800 g of the dried powder was mixed into a paste together with 1000 ml of Unimoll BB from the firm Bayer AG (benzyl butyl phthalate) at 2000 rev/min in a laboratory dissolver. 100 g samples of the ready-mixed paste were blended with each of the additives shown in Table 1. Then the time by which the initially liquid pastes had become doughy or rubbery was determined at the temperatures shown in Table 1.
Le A 30 216-Foreign Countries 13 ~14~7~
Table 1 . _ . .. .
~ Example Additive Parts Doughy or -- Doughy or Doughy or~ - 5 rubbery at rubbery at rubbery at No. 23& after 45C after 55C after days minutes minutes 6A No additive - 2 25 c 1 (:~n 6B 4.4'-diamino-3.3'- 1.2 ~ 90 > 3000 213 dimethyldicyclo-hexvlmethane 6C ZnO 2 8 30 c 5 Comp 6D Isophorone 2 10 32 < 10 ~nmp ~ mi na 6E 4,4-diaminodicyclo- 2 ~ 60 ~ 1300 154 hexylmethane (HOls) 6F Ethylene diamine 2 1 2 c 1 c~r 6G 4.4--diaminodicyclo- 1.2 > 60 ~ 1350 160 hexylmethane (BASF) 6H 1.3-bis(amino- 2 ~ 3 33 < 10 Comp. methyl)cyclohexane 6I Hexadecylamine 2 ~ 1 14 2 p 6K Additive from 6B 2 ~ 60 ~ 1400 41 reacted with isobutyraldehyde to the corresponding ~1 ~li mi n~o 6L 4.4--diamino- 2 - 43 Comp. diphenylmethane Le A 30 216-Foreign Countries 14
Plastisols and organosols which are stable in storage are known, for example, from EP-A 265 371. The plastisols and organosols described and claimed in the European patent application mentioned, compared with plastisols already known and discussed there as prior art, are distinguished by an improved stability in storage and by the fact that the plastisols and organosols claimed in the European patent application can be gelled at relatively low temperatures. The latter is achieved by the addition of multifunctional, basic substances which can be reacted with the finely divided carboxyl group-containing polymers in the dispersion.
Since plastisols and organosols are playing an increasingly important role in technology, for example, as sealants, as anticorrosive coatings for metals, for the impregnation and coating of substrates made of textiles, for cable insulating, as glues and for the production of composites, the technical demands on the plastisols and organosols,particularly as regards processability and stability in storage, are becoming ever higher.
Le A 30 216-Foreign Countries The object of the present invention is first, to improve in particular the stability in storage of the plastisols and organosols, even at higher ambient temperatures and second, to ensure good gelation at the lowest possible ambient temperatures. The object is fulfilled by using specific cycloaliphatic diamines for the production-of plastisols and organosols.
The invention therefore provides the use of cycloaliphatic diamines of the formula ~ R2 wherein R1, R2, R3, R4, R5 and R6 are identical or different and represent hydrogen or C1-C6 alkyl, preferably C1-C4 alkyl, R7 and R8 are identical or different and represent hydrogen, C1-C6 alkyl, preferably C1-C4 alkyl, or NR1R2 having the me~n;ngS given above for R and R , or represent OR or SR , n represents the numbers 1 to 6, preferably 1 to 4, and also the products of the reactions thereof with ketones, aldehydes and unsaturated or saturated carboxylic acids or carboxylic esters having 2 to 6 C atoms in the acid part and 1 to 4 C atoms in the ester part, Le A 30 216-Foreign Countries 2 . .
optionally in combination with metallic compounds reacting as bases, for the preparation of plastisols and organosols based on organic polymers and organic softeners.
For the preparation of plastisols and organosols, cyclo-aliphatic diamines of the formula R3 ~ R3 Rt ~ CH2 ~ N ~ 2 (II), R R~
wherein Rl to R4 having the me~n;ngs given in formula (I) are preferred, as well as the products of the reactions of the diamines of the formula (II) with ketones, aldehydes and unsaturated or saturated carboxylic acids or carboxylic esters having 2 to 6 carbon atoms in the acid part and 1 to 4 carbon atoms in the ester part.
The use of the following cycloaliphatic diamines is particularly preferred:
4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-diethyldicyclohexylmethane, 2,4,4'-triamino-5-methyldicyclohexylmethane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3,5-diethylcyclohexyl)methane or bis(4-amino-3-methyl-5-ethylcyclohexyl)methane.
Le A 30 216-Foreign Countries 3 ` ``~ 2144373 Besides the above-mentioned products of the reaction of the diamines with ketones, aldehydes and unsaturated or saturated carboxylic acids or carboxylic esters, the corresponding products of the addition of the cyclo-aliphatic diamines and oligomeric compounds to, for example, water, mineral acids (HCl, H2SO4) or glycols (for example, diethylene glycol) can also be used. The reaction of the cycloaliphatic diamines according to the invention with ketones, aldehydes and unsaturated carboxylic acids or carboxylic esters, and the addition of the above-mentioned compounds to the diamines according to the invention are known reactions and are generally described, for example, in Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Organo-Stickstoffverbindungen IV, Part 2, Volume E 16d, pages 646-1329.
The following may be given as examples of ketones, aldehydes, unsaturated carboxylic acids or carboxylic esters which are suitable for the above-mentioned reaction with the diamines according to the invention: isobutyraldehyde, fumaric acid ethyl ester, maleic acid, acetic acid; isobutyraldehyde is preferred. Suitable compounds for addition to the diamines are water, hydrochloric acid, sulphuric acid, preferably water.
The cycloaliphatic diamines according to the invention, the reaction products thereof and the addition products thereof can be used both individually and in mixtures with one another for the preparation of plastisols and organosols.
It is moreover possible to use the cycloaliphatic diamines according to the invention or the reaction products or addition products thereof together with basic metallic compounds for the preparation of plastisols and organosols. In particular zinc oxide, calcium carbonate, magnesium oxide, magnesium carbonate and calcium stearate are suitable basic Le A 30 216-Foreign Countries 4 metallic compounds; zinc oxide and calcium stearate are particularly preferred.
The cycloaliphatic diamines according to the invention and the reaction products and addition products thereof (for brevity referred to below as "diamines according to the invention") can be used in quantities of from 0.1 to 20% by weight, referred to the quantity of polymer. The diamines according to the invention are preferably used in quantities of from 0.5 to 5% by weight.
If basic metallic compounds are used concomitantly in the preparation of plastisols and organosols, these can be used in quantities of from 0.5 to 150% by weight, referred to the quantity of polymer, particularly in quantities of from 1 to 50%
by welght.
Plastisols are in general dispersions of finely divided resins in plasticizers (i.e. softeners). Usually plastisols are in the paste form at normal temperatures and become gels when heated to certain temperatures as a result of solvation of the resin particles by the plasticizers. If volatile solvents are included, the plastisols are called as organosols (see Hawley's Condensed Chemical Dictionary, Twelfth Edition, by Richard J. Lewis, Jr. - Van Nostrand Reinhold Company, New York).
Plastisols and organosols which are particularly suitable for stabilisation by the diamines according to the invention are copolymers, in the form of finely divided particles, of any monomers and polymerisable acids, for example, copolymers of vinyl chloride, vinylidene chloride, acrylates, methacrylates, maleates, styrene, methylstyrene, acrylamides, vinyl esters, methacrylonitrile, vinyl ethers, acrylonitrile, olefins or dienes with polymerisable acids such as, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid. Preferred plastisols are those based on styrene-acrylonitrile (SAN) resins containing a proportion of from 5 to 60% by weight of acrylonitrile, preferably from 5 to 40% by weight, particularly from 10 to 35%
by weight, wherein the SAN resin advantageously still contains a small quantity of acid (from 0.5 to 15% by weight, particularly 2 to 7% by weight). Also preferred are plastisols based on polyvinyl chloride and polymethacrylates as well as the copolymers thereof. Some of them are commercially available, for example, Vestolit E type polyvinyl chloride available from Huls AG of Germany, Plex 4944 polymethyl methacrylate available from Rohm & Haas of U.S.A. and Geon 137 polyvinyl chloride available from Goodrich of U.S.A. which contains approximately 6% of acrylic acid.
Suitable organic plasticizers (softeners) are high-boiling organic solvents which function as softeners at an elevated temperature, such as are already known in the preparation of plastisols and organosols. In this connection reference is made to DE 24 54 235 and EP 265 371. The plasticizer, i.e. the liquid phase, used can be any liquid which brings about the abovementioned gelation at elevated temperatures. It is important for this liquid to have very low volatility, since otherwise the plasticizer could gradually * Trade-mark escape during the storage of the completely gelled plastisols and undesirable changes in their properties could occur.
Commercially important plasticizers are for example the esters of phthalic, adipic, sebacic, phosphoric and citric acid, chlorinated hydrocarbons, liquid polyesters and epoxidised natural oils such as linseed oil or soybean oil. High-boiling polymerizable liquids which are copolymerized during gelation such as multifunctional acrylic or allyl compounds, can also be used as plasticizers. Such plasticizers are for example higher-boiling, predominantly polyfunctional acrylic or allylcompounds. A comprehensive definition of the plasticizer and an explanation of the chemical and physical interactions which occur between a plasticizer and a polymer can be found in:
"Beschichten mit Lacken und Kunststoffen" (Coating with lacquers and plastics), K. Weinmann (Verlag W.A. Colom, Stuttgart, 1967), pages 47 to 158.
A certain quantity of volatile solvents can be added to the plastisols according to the invention to regulate their processing properties. If the content of volatile solvents is about 5 to 10% the plastisols are referred to as organosols (cf.
for example H.A. Sarvertnick, "Plastisols and organosols", page 201, Nostrand Reinhold Company, New York 1972).
The quantity of the plasticizers is usually from 30 to 150 parts by weight, preferably ~rom 80 to 120 parts by weight per 100 parts by weight of the organic polymer used.
6a `- 2144373 The present invention therefore also provides plastisols and organosols based on organic polymers and organic plasticizers, which contain cycloaliphatic diamines of the formula 214~373 ~N ~ R2 wherein R1, R2, R3, R4, R5, R6, R7 and R8 and n have the me~n; ngs previously given, and also the products of the reactions thereof with ketones, aldehydes and unsaturated or saturated carboxylic acids or carboxylic esters having 2 to 6 carbon atoms in the acid part and 1 to 4 carbon atoms in the ester part, and optionally basic metallic compounds.
The plastisols and organosols according to the invention are prepared in a conventional manner by mixing the organic polymers with the organic softeners and the cycloaliphatic diamines according to the invention. The mixing of the paste is carried out in a manner known to the person skilled in the art. The stabilising additives are dissolved or dispersed in the softeners in an appropriate manner. In individual cases it may be advantageous to store the ready-mixed paste for 10 to 48 hours at 5 to 15C prior to further processing.
Besides the diamines mentioned according to the invention, other additives can be added to the plastisols and organosols according to the invention, such as inert fillers, for Le A 30 216-Foreign Countries 7 214437~
example, chalks, heavy spar, kaolin, highly dispersed silica powders, aluminium silicates, talc, glass powder, sand, aluminium oxide and aluminium hydroxide, antimony trioxide, metal soaps, titanium dioxide, carbon black, dyes, pigments and all kinds of surface-treated (e.g. silanised) fillers and pigments, as well as corrosion inhibitors, agents for controlling viscosity, stabilisers against heat, light and oxidation, expanding agents and bonding agents. In this connection, reference is made to DE 24 54 235. Suitable bonding agents are those known to persons skilled in the art, such as for example: one- and two-component isocyanate bonding agents (Desmodur, Desmophen and Desmocap, from Bayer), preferably blocked systems, epoxy bonding agent systems (from Ciba), and polyaminoamides (such as for example the Euretek types from Witco or the Nourybond types from Akzo), resorcinol-cont~;n;ng systems and free-radical polymerisable monomers such as triethylene glycol dimethacrylate.
The bonding agent can be appropriately dispersed in the paste or already applied to the polymer particles during the processing of the latex - during the spray-drying process. If importance is attached to a combination of adhesion and sufficient storability, all the known bonding agents can be used which have a sufficiently low reactivity towards the stabilising additives of formula I to prevent any undesired reaction between the bonding agent component and the stabilising additive. Polyaminoamides and blocked isocyanates are particularly suitable bonding agents for this purpose. Due to the crosslinking reaction of the diamine with for example isocyanates an additional positive effect can be obtained as the mechanical properties, apart from the higher storability.
The additives mentioned can be added to the plastisols and organosols according to the invention in quantities of from Le A 30 216-Foreign Countries 8 ~ 2144373 0.5 to 250% by weight, preferably from 15 to 150% by weight, referred to the polymer used. The optimal quantity can be easily established by appropriate prel;min~ry tests.
The plastisols according to the invention are particularly suitable as sealants, as anticorrosive coatings for metals, coated sheets, for the impregnation and coating of substrates made of textiles or paper, for cable insulating, as glues and for the production of composites.
Le A 30 216-Foreign Countries 9 ` 214~373 Exam~les Exam~le~ lA ~na lB:
A spray-dried emulsion polymer consisting of 59 parts of styrene, 25 parts of acrylonitrile, 10 parts of butyl acrylate and 6 parts of acrylic acid is used to prepare a paste with Unimol~ BB (benzyl butyl phthalate, BayerJ:
lA: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) lB: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 5 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane Both pastes are thinly viscous ;mme~iately after preparation.
After storage at 23C, the sample lA is highly viscous or rubbery after 48 hours, whilst the sample lB remains pasty for at least 90 days. Both samples can be gelled at temperatures of from 130 to 160C to form soft, elastic rubber gels, while the sample supplied with the additive (gelation at 160C) shows distinctly improved mechanical properties.
lA lB
Strength 0.85 3.71 (MPa) (determined according to DIN 53 455) Elongation 660 286 (~) (determined according to DIN 53 455) * Trade-mark `~ 21g4373 ~x~m~le8 2A ~nd 2s A spray-dried emulsion polymer consisting of 64 parts of styrene, 10 parts of acrylonitrile, 20 parts of butyl acrylate and 6 parts of acrylic acid is used to prepare a paste:
2A: 40 g of polymer 60 g of di-2-ethyl hexyl phthalate 2B: 40 g of polymer 60 g of di-2-ethyl hexyl phthalate 2 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane Both the samples were obtained in the form of pastes of low viscosity. The pastes are first of all stored at 8C for 24 h.
This is followed by storage at 45C. While the sample 2A has already gelled after 2 minutes, the sample 2B can be stored for 4 hours without gelling completely. Both samples can be gelled at temperatures of from 130 to 160C to form soft, elastic rubber gels.
Rxam~le~ 3A ~nd 3s A brand of E-PVC (Vestolit E 7012, Huls AG, Germany) was mixed with benzyl butyl phthalate (Unimoll BB) in a dissolver to form a paste of low viscosity:
3A: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 3B: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 2 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane * Trade-mark , 11 .
214~37~
231~9-7749 The test of the storability is carried out in a viscometer at a constant rate of rotation of 400 rev/min and measurements are taken at a temperature of 55C. Whilst the paste 3A
already shows a distinct increase in viscosity after 41 minutes, the sample 3B remains llnchAnged for 5 hours.
Ex~mol~ ~ ~n~ 41~
A PMMA brand of paste from the firm Rahm, Germany (Plex 4944 F) was made into a paste with Unimoll BB, Bayer AG, in a dissolver:
4A: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 4B: 40 g of polymer 60 g of benzyl butyl phthalate (Unimoll BB) 2 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane Both pastes are doughy immediately after preparation. After storage at 55C, the sample 4A has gelled after 75 minutes, whilst the sample 4B remains pasty to mouldable for at least 3 hours. Both samples can be gelled at temperatures of from 140 to 160C to form soft, elastic rubber gels.
Ex~moleR 5A ~n~ 5~
A spray-dried emulsion polymer consisting of 59 parts of styrene, 25 parts of acrylonitrile, lO parts of butyl acrylate and 6 parts of acrylic acid is used to prepare a paste with MesamoIl*(alkylsulphonic ester, Bayer) as softener:
SA: 40 g of p~lymer 60 g of alkylsulphonic ester (Mesamoll, Bayer) * Trade-mark 214~373 5B: 40 g of polymer 60 g of alkylsulphonic ester (Mesamoll, Bayer) 5 g of 4,4'-diamino-3,3'-dimethyldicyclohexylmethane Both pastes are thinly viscous immediately after preparation.
After storage at 55C, the sample 5A is highly viscous or rubbery after 150 minutes, whilst the sample 5B r~m~;ns pasty to doughy at 65C for at least 1100 minutes. Both samples can be gelled at temperatures of from 130 to 160C to form soft, elastic rubber gels.
~camDles 6A to 6I.
2000 ml of latex of an emulsion polymer consisting of 25% ACN, 6% acrylic acid, 10% butyl acrylate and 59% styrene was worked up by spray drying. 800 g of the dried powder was mixed into a paste together with 1000 ml of Unimoll BB from the firm Bayer AG (benzyl butyl phthalate) at 2000 rev/min in a laboratory dissolver. 100 g samples of the ready-mixed paste were blended with each of the additives shown in Table 1. Then the time by which the initially liquid pastes had become doughy or rubbery was determined at the temperatures shown in Table 1.
Le A 30 216-Foreign Countries 13 ~14~7~
Table 1 . _ . .. .
~ Example Additive Parts Doughy or -- Doughy or Doughy or~ - 5 rubbery at rubbery at rubbery at No. 23& after 45C after 55C after days minutes minutes 6A No additive - 2 25 c 1 (:~n 6B 4.4'-diamino-3.3'- 1.2 ~ 90 > 3000 213 dimethyldicyclo-hexvlmethane 6C ZnO 2 8 30 c 5 Comp 6D Isophorone 2 10 32 < 10 ~nmp ~ mi na 6E 4,4-diaminodicyclo- 2 ~ 60 ~ 1300 154 hexylmethane (HOls) 6F Ethylene diamine 2 1 2 c 1 c~r 6G 4.4--diaminodicyclo- 1.2 > 60 ~ 1350 160 hexylmethane (BASF) 6H 1.3-bis(amino- 2 ~ 3 33 < 10 Comp. methyl)cyclohexane 6I Hexadecylamine 2 ~ 1 14 2 p 6K Additive from 6B 2 ~ 60 ~ 1400 41 reacted with isobutyraldehyde to the corresponding ~1 ~li mi n~o 6L 4.4--diamino- 2 - 43 Comp. diphenylmethane Le A 30 216-Foreign Countries 14
Claims (15)
1. A method for a preparation of a plastisol or organosol based on an organic polymer and a plasticizer, which comprises admixing with the organic polymer and the plasticizer, a storage stability enhancing effective amount of one member selected from the group consisting of:
(a) a cycloaliphatic diamine of the formula:
(I), (wherein R1, R2, R3, R4, R5 and R6 are identical or different and represent hydrogen or C1-C6 alkyl, R7 and R8 are identical or different and represent hydrogen, C1-C6 alkyl, NR1R2, OR1 or SR1 [in which R1 and R2 have the meanings given above], and n represents a number 1 to 6) (b) an adduct of the cycloaliphatic diamine (a) with water, a mineral acid or a glycol, (c) a reaction product of the cycloaliphatic diamine (a) with a ketone, aldehyde, unsaturated or saturated carboxylic acid having 2 to 6 C atoms or ester thereof having 1 to 4 C atoms in the ester part, and (d) a combination of any one or (a), (b) and (c) with a basic metallic compound.
(a) a cycloaliphatic diamine of the formula:
(I), (wherein R1, R2, R3, R4, R5 and R6 are identical or different and represent hydrogen or C1-C6 alkyl, R7 and R8 are identical or different and represent hydrogen, C1-C6 alkyl, NR1R2, OR1 or SR1 [in which R1 and R2 have the meanings given above], and n represents a number 1 to 6) (b) an adduct of the cycloaliphatic diamine (a) with water, a mineral acid or a glycol, (c) a reaction product of the cycloaliphatic diamine (a) with a ketone, aldehyde, unsaturated or saturated carboxylic acid having 2 to 6 C atoms or ester thereof having 1 to 4 C atoms in the ester part, and (d) a combination of any one or (a), (b) and (c) with a basic metallic compound.
2. A method according to claim 1, wherein from 0.1 to 20%
by weight of the member (a), (b), (c) or (d) is used based on the polymer.
by weight of the member (a), (b), (c) or (d) is used based on the polymer.
3. A method according to claim 2, wherein the member (a), (b), (c) or (d) is admixed with a paste made of finely divided particles of a copolymer of at least one non-acid monomer selected from the group consisting of vinyl chloride, vinylidene chloride, acrylates, methacrylates, maleates, styrene, methylstyrene, acrylamides, vinyl esters, methacrylonitrile, vinyl ethers, acrylonitrile, olefins and dienes with 0.5 to 15%
by weight (based on the copolymer) of at least one polymerizable acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid, and a high boiling organic solvent which acts as a softener of the polymer at an elevated temperature.
by weight (based on the copolymer) of at least one polymerizable acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid, and a high boiling organic solvent which acts as a softener of the polymer at an elevated temperature.
4. A method according to claim 3, wherein the copolymer is styrene-acrylonitrile resin having an acrylonitrile content of 5 to 60% by weight and a polymerizable acid content of 0.5 to 15% by weight.
5. A method according to claim 3, wherein the non-acid monomer is vinyl chloride.
6. A method according to claim 3, wherein the non-acid monomer is a methacrylate.
7. A method according to claim 3, wherein the non-acid monomer is a combination of styrene, acrylonitrile and an acrylate; and the polymerizable acid is acrylic acid.
8. A method according to claim 3, wherein the high boiling solvent is a phthalate.
9. A method according to any one of claims 1 to 8, wherein the cyclo aliphatic diamine (a) is used and is 2,4,4'-triamino-5-methyldicyclohexylmethane or a diamine of the formula:
(II)' (wherein R1, R2, R3 and R4 each represent hydrogen or C1-C4 alkyl).
(II)' (wherein R1, R2, R3 and R4 each represent hydrogen or C1-C4 alkyl).
10. A method according to claim 9, wherein the cycloaliphatic diamine (a) is 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-diethyldicyclohexylmethane, 2,4,4'-triamino-5-methyldicyclohexylmethane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3,5-diethylcyclohexyl)methane or bis(4-amino-3-methyl-5-ethylcyclohexyl)methane.
11. A method according to any one of claims 1 to 8, wherein the reaction product (c) is used, the reaction product being produced by reacting a cycloaliphatic diamine which is 2,4,4'-triamino-5-methyldicyclohexylmethane or a diamine of the formula:
(II), (wherein R1, R2, R3 and R4 each represent hydrogen or C1-C4 alkyl) with isobutylaldehyde, fumaric acid ethyl ester, maleic acid or acetic acid.
(II), (wherein R1, R2, R3 and R4 each represent hydrogen or C1-C4 alkyl) with isobutylaldehyde, fumaric acid ethyl ester, maleic acid or acetic acid.
12. A method according to any one of claims 1 to 8, wherein the combination (d) is used and it is a combination of any one of (a), (b) and (c) with a basic metallic compound selected from the group consisting of zinc oxide, calcium carbonate, magnesium oxide, magnesium carbonate and calcium stearate, the basic metallic compound being in an amount of 0.5 to 150% by weight based on the polymer.
13. A plastisol or organosol, which comprises [I] an organic polymer and an organic plasticizer, and [II] 0.1 to 20%
by weight (based on the polymer) of one member selected from the group consisting of:
(a) a cycloaliphatic diamine of the formula:
(I), (wherein R1, R2, R3, R4, R5 and R6 are identical or different and represent hydrogen or C1-C6 alkyl, R7 and R8 are identical or different and represent hydrogen, C1-C6 alkyl, NR1R2, OR1 or SR1 [in which R1 and R2 have the meanings given above], and n represents a number 1 to 6) (b) an adduct of the cycloaliphatic diamine (a) with water, a mineral acid or a glycol, (c) a reaction product of the cycloaliphatic diamine (a) with a ketone, aldehyde, unsaturated or saturated carboxylic acid having 2 to 6 C atoms or ester thereof having 1 to 4 C atoms in the ester part, and (d) a combination of any one of (a), (b) and (c) with a basic metallic compound.
by weight (based on the polymer) of one member selected from the group consisting of:
(a) a cycloaliphatic diamine of the formula:
(I), (wherein R1, R2, R3, R4, R5 and R6 are identical or different and represent hydrogen or C1-C6 alkyl, R7 and R8 are identical or different and represent hydrogen, C1-C6 alkyl, NR1R2, OR1 or SR1 [in which R1 and R2 have the meanings given above], and n represents a number 1 to 6) (b) an adduct of the cycloaliphatic diamine (a) with water, a mineral acid or a glycol, (c) a reaction product of the cycloaliphatic diamine (a) with a ketone, aldehyde, unsaturated or saturated carboxylic acid having 2 to 6 C atoms or ester thereof having 1 to 4 C atoms in the ester part, and (d) a combination of any one of (a), (b) and (c) with a basic metallic compound.
14. The plastisol according to claim 13, which is a paste made by admixing the member (a), (b), (c) or (d) with finely divided particles of a copolymer of at least one non-acid monomer selected from the group consisting of vinyl chloride, vinylidene chloride, acrylates, methacrylates, maleates, styrene, methylstyrene, acrylamides, vinyl esters, methacrylonitrile, vinyl ethers, acrylonitrile, olefins and dienes with 0.5 to 15% by weight (based on the copolymer) of at least one polymerizable acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid, and a high boiling organic solvent which acts as a softener of the polymer at an elevated temperature.
15. The organosol according to claim 13, which is a paste made by admixing the member (a), (b), (c) or (d) with finely divided particles of a copolymer of at least one non-acid monomer selected from the group consisting of vinyl chloride, vinylidene chloride, acrylates, methacrylates, maleates, styrene, methylstyrene, acrylamides, vinyl esters, methacrylonitrile, vinyl ethers, acrylonitrile, olefins and dienes with 0.5 to 15% by weight (based on the copolymer) of at least one polymerizable acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid, and a high boiling organic solvent which acts as a softener of the polymer at an elevated temperature as well as a volatile solvent, the amount of the volatile solvent being from about 5 to about 10% by weight of the organosol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4408728.4 | 1994-03-15 | ||
| DE19944408728 DE4408728A1 (en) | 1994-03-15 | 1994-03-15 | Use of cycloaliphatic diamines for the production of storage-stable plastisols and organosols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2144373A1 true CA2144373A1 (en) | 1995-09-16 |
Family
ID=6512825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2144373 Abandoned CA2144373A1 (en) | 1994-03-15 | 1995-03-10 | Use of cycloaliphatic diamines for the preparation of plastisols and organosols which are stable in storage |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0672714A1 (en) |
| JP (1) | JPH08319355A (en) |
| CA (1) | CA2144373A1 (en) |
| DE (1) | DE4408728A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009147025A2 (en) * | 2008-06-04 | 2009-12-10 | Basf Se | Method for the production of organosols |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2232885C3 (en) * | 1972-07-05 | 1981-11-19 | Röhm GmbH, 6100 Darmstadt | Polyvinyl chloride plastisol |
| DE3403497A1 (en) * | 1984-02-02 | 1985-08-08 | Bayer Ag, 5090 Leverkusen | ADHESIVE ADDITIVES CONTAINING PVC PLASTISOLS FOR COATING PURPOSES AND THEIR USE |
| DE3442646C2 (en) * | 1984-11-22 | 1986-10-23 | Dr. Alois Stankiewicz GmbH, 3101 Adelheidsdorf | Polyvinyl chloride free plastisol and its uses |
-
1994
- 1994-03-15 DE DE19944408728 patent/DE4408728A1/en not_active Withdrawn
-
1995
- 1995-03-02 EP EP95102963A patent/EP0672714A1/en not_active Withdrawn
- 1995-03-10 JP JP7983495A patent/JPH08319355A/en active Pending
- 1995-03-10 CA CA 2144373 patent/CA2144373A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE4408728A1 (en) | 1995-09-21 |
| JPH08319355A (en) | 1996-12-03 |
| EP0672714A1 (en) | 1995-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1970418B1 (en) | Water-based one-pack-type coating composition and coated article | |
| US20040059023A1 (en) | Method for synthesis of spray-dried poly(METH)acrylate polymers, use of same as polymer components for plastisols, and plastisols produced therewith | |
| US11168230B2 (en) | High block, tack and scrub resistant coating composition | |
| US10273378B2 (en) | High block, tack and scrub resistant coating composition | |
| JP2004018859A (en) | Curable composition | |
| US4613639A (en) | Preparation of plastisols and organosols having a long shelf life | |
| JP2634822B2 (en) | Plastisol based on styrene / acrylonitrile copolymer | |
| US4673703A (en) | Coating compositions | |
| US6495626B1 (en) | Plastisol compositions with two dissimilar acrylic polymer components | |
| EP0534847B1 (en) | Plastisol compositions | |
| US5120795A (en) | Nonaqueous plastics formulations | |
| JPH0692566B2 (en) | Dispersion type paint resin composition | |
| CA2144373A1 (en) | Use of cycloaliphatic diamines for the preparation of plastisols and organosols which are stable in storage | |
| US5425997A (en) | Fatty acid modified alkyd coatings with improved substrate adhesion | |
| JPH10168268A (en) | Spray-dried polymer for pmma plastisol having improved storage stability | |
| JPH0269507A (en) | Dispersing unit composition for ambient temperature curing type coating | |
| US3414534A (en) | Adhesive compositions comprising vinyl chloride polymer, polymerizable material and lead containing stabilizer | |
| EP0635552B1 (en) | Coating compositions | |
| EP0212771A1 (en) | Viscosity stable plastisol sealant | |
| JPH0662822B2 (en) | Chlorinated ethylene copolymer latex | |
| TWI273124B (en) | Surface treating additive, surface treating composition thereof, and its application | |
| JP4280646B2 (en) | Wall remodeling method | |
| WO1998035994A1 (en) | Water-based emulsion polymers which resist blocking | |
| KR19980071124A (en) | Vehicles for paints and varnishes formulated with vinylidene fluoride-hexafluoropropylene copolymer | |
| DE4400509A1 (en) | plastisol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |