Source: https://patents.justia.com/patent/4879337
Timestamp: 2019-11-12 01:18:46
Document Index: 138038351

Matched Legal Cases: ['art)\n17', 'art)\n18', 'art)\n17', 'art)\n18', 'art)\n17', 'art)\n18', 'art)\n55', 'arts\n154', 'arts\n3', 'art\n3', 'arts\n142', 'arts   70', 'arts\n92', 'arts\n3', 'arts 1298', 'arts\n592', 'arts 592', 'arts\n74', 'arts  186', 'arts 142', 'arts\n5', 'arts\n2', 'arts\n40', 'arts\n2', 'arts     3000']

US Patent for Polyol resin coating composition containing non-aqueous polymer dispersion and aliphatic sulfonic acid compound Patent (Patent # 4,879,337 issued November 7, 1989) - Justia Patents Search
Justia Patents Solid Graft Or Solid Graft-type Copolymer With Other Solid Polymer, Sicp, Or SpfiUS Patent for Polyol resin coating composition containing non-aqueous polymer dispersion and aliphatic sulfonic acid compound Patent (Patent # 4,879,337)
Nov 2, 1987 - Nippon Oil and Fats Co., Ltd.
A higher solid coating composition comprises a solid resin mixture of polyol resin and alkyletherified melamine resin, 0.2.about.10 parts by weight of an aliphatic sulfonic acid compound and 1.about.100 parts by weight of a non-aqueous polymer dispersion based on 100 parts by weight of the resin mixture. The non-aqueous polymer dispersion consists of (a) organic solvent component, (b) particle component insoluble in the component (a), and (c) particular dispersion stabilizer component soluble in the component (a) and capable of stably dispersing the component (b) into the component (a).
Polarity of particle  high     low
Polarity of dispersion stabilizer
In the relation (B), vinyl type monomer forming particles must have a low polarity. However, since the glass transition temperature is usually low in the polymerization of such a low polarity vinyl type monomer, the particles made from the vinyl type monomer become fairly soft. On the other hand, the synthesis of the non-aqueous polymer dispersion is usually carried out by radical polymerization, so that the temperature in the synthesis is frequently more than about 60.degree. C. Therefore, the relation (B) is not so favorable because there is a high possibility of causing the fusing between particles in the synthesis of the non-aqueous polymer dispersion.
According to the invention, there is the provision of a higher solid coating composition, comprising 100 parts by weight of a solid resin mixture composed of 30.about.90 parts by weight of a polyol resin and 10.about.70 parts of weight of an alkyletherified melamine resin, 0.2.about.10 parts by weight of an aliphatic sulfonic acid compound having a carbon number of 4.about.22 as an aliphatic sulfonic acid, and 1.about.100 parts by weight as a polymer solid content of a non-aqueous polymer dispersion consisting of 40.about.80% by weight of (a) an organic solvent component, 10.about.50% by weight of (b) a particle component insoluble in the component (a) and 5.about.40% by weight of (c) a dispersion stabilizer component soluble in the component (a) and capable of stably dispersing the component (b) into the component (a);
said dispersion stabilizer component being preferably obtained by polymerizing 20.about.100% by weight of a vinyl type monomer containing polyester chain group of the following general formula with 0.about.80% by weight of a second vinyl type monomer: ##STR1## wherein X is a hydrogen atom or a methyl group, Y is ##STR2## m and n are 1.about.10, respectively, R.sub.1 is a residue of acid anhydride having a carbon number of 2.about.6, R.sub.2 is a phenyl group, an alkyl or aromatic group having a carbon number of 5.about.19, ##STR3## group (R.sub.5 is an alkyl or aromatic group having a carbon number of 3.about.17), or --CH.sub.2 --O--R.sub.6 group (R.sub.6 is an alkyl or aromatic group having a carbon number of 4.about.18), R.sub.3 is an alkyl group or a residue of aromatic monocarboxylic acid having a carbon number of 1.about.20, and R.sub.4 is a residue of saturated aliphatic, alicyclic or aromatic monovalent alcohol having a carbon number of 1.about.18.
As the mixing ratio of polyol resin to alkyletherified melamine resin, it is necessary that the alkyletherified melamine resin is within a range of 10.about.70 parts by weight to 30.about.90 parts by weight of the polyol resin.
For instance, the following aliphatic sulfonic acid salts may be mentioned as a starting material: ##STR4## wherein R.sup.1 is an alkyl group having a carbon number of 8.about.22, R.sup.2 is an alkyl group having a carbon number of 4.about.8 and R.sup.3 is an alkyl group having a carbon number of 13.about.17.
These aliphatic sulfonic acid salts can be converted into respective free acids through the removal of sodium or potassium with an inorganic acid. Moreover, the aliphatic sulfonic acid salt having a carbon number of less than 4 has a difficult point in the solubility in organic solvent likewise the case of the conventional aromatic sulfonic acid. As the inorganic acid, use may be made of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and so on. In this case, the amount of the inorganic acid used is not restricted, but it is preferably within a range of 0.5.about.1.5 times to equivalent of aliphatic sulfonic acid salt for preventing the film performances, particularly water resistance of the resulting coated film. When the amount of the inorganic acid is less than 0.5 equivalent, the unreacted aliphatic sulfonic acid salt remains, while when it exceeds 1.5 equivalent, byproducts are produced from the aliphatic sulfonic acid salt, resulting in the undesirable reduction of water resistance of the coated film. The removal of sodium or potassium can quantitatively be carried out at room temperature according to the usual manner.
The amount of aliphatic sulfonic acid compound added can optionally be determined in accordance with the objective film performances, but it is used within a range of 0.2.about.10 parts by weight, preferably 0.4.about.8 parts by weight as aliphatic sulfonic acid per 100 parts by weight as a resin solid of a mixture of polyol resin and alkyletherified melamine resin likewise the case of the conventional aromatic sulfonic acid compound. When the addition amount is less than 0.1 part by weight, the acid catalyst effect is not effectively developed, while when it exceeds 10 parts by weight, the water resistance of the coated film undesirably lowers.
That is, the first method is as follows. A monocarboxylic acid of R.sub.3 --COOH and a monofunctional epoxy compound of ##STR5## are esterified at 100.degree..about.180.degree. C., preferably 120.degree..about.160.degree. C. and then the resulting secondary hydroxyl group is esterified with an acid anhydride of ##STR6## at 100.degree..about.180.degree. C., preferably 120.degree..about.160.degree. C. to obtain a reaction intermediate having a carboxyl group in terminal of molecule. Thereafter, the carboxyl group of the reaction intermediate is esterified with a monofunctional epoxy compound of ##STR7## under the above condition and further the resulting secondary hydroxyl group is esterified with an acid anhydride of ##STR8## under the above condition to obtain a reaction intermediate having a carboxyl group in terminal of molecule having polyester chain longer than that of the aforementioned reaction intermediate. Such a reaction procedure is repeated 1.about.10 times to obtain a polyester compound having a carboxyl group in terminal of molecule with a given molecular weight. Then, the carboxyl group of the resulting polyester compound is esterified with a vinyl type monomer containing glycidyl group such as glycidyl acrylate, glycidyl methacrylate or the like at 80.degree..about.160.degree. C., preferably 100.degree..about.140.degree. C. to obtain a vinyl type monomer containing polyester chain group.
The second method is as follows. A monovalent alcohol of R.sub.4 --OH and an acid anhydride of ##STR9## are esterified at 100.degree..about.180.degree. C., preferably 120.degree..about.160.degree. C. to obtain a reaction intermediate having a carboxyl group in terminal of molecule. Then, the reaction intermediate is repeatedly subjected to successive esterification reaction with a monofunctional epoxy compound of ##STR10## and with an acid anhydride of ##STR11## 1.about.10 times in the same manner as in the first method to obtain a polyester compound having a carboxyl group in terminal of molecule. Thereafter, the carboxyl group of the resulting polyester compound is esterified with the aforementioned vinyl type monomer containing glycidyl group at 80.degree..about.160.degree. C., preferably 100.degree..about.140.degree. C. to obtain a vinyl type monomer containing polyester chain group.
As the monofunctional epoxy compound represented by ##STR14## in the first and second methods, mention may be made of styrene oxide having a phenyl group; phenyl glycidylether, p-tolyl glycidylether or n-butyl glycidylether having a glycidylether group; versatic acid glycidylester or p-tert-butyl benzoic acid glycidylester having a glycidylester group; .alpha.-olefin oxide having an alkyl group, and the like.
As the monocarboxylic acid represented by R.sub.3 --COOH in the first method, mention may be made of acetic acid, propionic acid, caprylic acid, nonanic acid, caprilic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isononanic acid, 2-ethyl hexanoic acid, arachic acid having an alkyl group; benzoic acid, p-tert-butyl benzoic acid having an aromatic group, and the like.
As the monovalent alcohol represented by R.sub.4 --OH in the second method, mention may be made of saturated aliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, stearyl alcohol; alicyclic alcohols such as cyclopentanol, cyclohexanol; aromatic alcohols such as benzyl alcohol, p-tert-butyl benzyl alcohol, and the like.
In the first and second methods, the esterification reaction between hydroxy group and acid anhydride and the esterification reaction between carboxyl group and monofunctional epoxy compound are carried out at a temperature of 100.degree..about.180.degree. C., preferably 120.degree..about.160.degree. C. When the reaction temperature is lower than 100.degree. C., the long reaction time is required, while when it exceeds 180.degree. C., the side reaction such as dehydration or the like is unfavorably caused to lower the dispersion stability of the resulting non-aqueous polymer dispersion. In these esterification reactions, an ordinary catalyst for the esterification such as N,N-dimethyl benzylamine, dimethyl laurylamine, triphenylphosphine or the like may be used for completing the esterification reaction in a shorter time. On the other hand, the esterification reaction between polyester compound having the carboxyl group in terminal of molecule and vinyl type monomer containing glycidyl group in the first and second methods is carried out at a temperature of 80.degree..about.160.degree. C., preferably 100.degree..about.140.degree. C. The vinyl type monomer containing glycidyl group includes glycidyl acrylate and glycidyl methacrylate. When the reaction temperature is lower than 80.degree. C., the long reaction time is required, while when it exceeds 160.degree. C., the vinyl group is unfavorably thermal-polymerized to lower the dispersion stability of the resulting non-aqueous polymer dispersion. This esterification can be completed in a shorter time by using the ordinary esterification catalyst as mentioned above.
The dispersion stabilizer component in the non-aqueous polymer dispersion is used in an amount of 5.about.40% by weight based on the total weight of the non-aqeuous polymer dispersion. When the amount of the dispersion stabilizer is less than 5% by weight, the dispersion stability of the resulting non-aqueous polymer dispersion is insufficient and the particle components are agglomerated. while when it exceeds 40% by weight, the formation of particle component is insufficient and the fluidity controlling function when being applied to a higher solid coating is insufficient.
As the organic solvent component used in the non-aqueous polymer dispersion according to the invention, use may be made of any organic solvents dissolving the dispersion stabilizer but exhibiting insolubility against the particle component, an example of which includes aliphatic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, n-heptane, n-octane, mineral spirit and the like; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and the like; alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and the like; acetic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate and the like; ketones such as acetone, methylethyl ketone, methylisobutyl ketone, methylamyl ketone, cyclohexanone, isophorone and so on. These organic solvents may be used alone or in admixture. In order to stably produce the non-aqueous polymer dispersion, however, the organic solvent is necessary to have a polarity lower than that of the particle component within a range dissolving the dispersion stabilizer component. Furthermore, the amount of the organic solvent used is required to be within a range of 40.about.80% by weight based on the total weight of the non-aqueous polymer dispersion. When the amount is less than 40% by weight, the dispersion stability of the resulting non-aqueous polymer dispersion is insufficient and the particle components are agglomerated, while when it exceeds 80% by weight, it is required to concentrate the resulting non-aqueous polymer dispersion and hence the production efficiency of the dispersion undesirably lowers.
The non-aqueous polymer dispersion used in the invention is obtained by dissolving the dispersion stabilizer component into the organic solvent component and then polymerizing in the resulting solution a vinyl type monomer as a starting material for particle component insoluble in the component (a). As the vinyl type monomer to be polymerized, one or more of the second vinyl type monomers used in the formation of the dispersion stabilizer component may optionally be selected, but it is necessary to use the vinyl type monomer having a polarity higher than that of the dispersion stabilizer component in order to stably produce the non-aqueous polymer dispersion. In this case, the particle component is formed in an amount of 10.about.50% by weight based on the total weight of the non-aqueous polymer dispersion. When the amount is less than 10% by weight, the formation of particle component is insufficient and the fluidity controlling function when being applied to a higher solid coating is insufficient, while when it exceeds 50% by weight, the dispersion stability of the resulting non-aqueous polymer dispersion is insufficient and the particle components are undesirably agglomerated.
The thus obtained non-aqueous polymer dispersion is used in an amount of 1.about.100 parts by weight as a polymer solid content based on 100 parts by weight of a solid resin mixture of polyol resin and alkyletherified melamine resin. When the amount as polymer solid content is 1 part by weight, the fluidity controlling function for the higher solid coating is insufficient, while when it exceeds 100 parts by weight, the chemical resistance of the resulting coated film undesirably lowers.
The thus obtained coating is applied to an ordinary substrate such as metal or other inorganic substrate, plastics or other organic substrate by the usual application process such as air spraying, airless spraying, electrostatic spraying, diping or the like, and then dried by baking to form a coated film thereon. In this case, it is preferable that the baking and drying are carried out under such a condition that aliphatic sulfonic acid is isolated from the aliphatic sulfonic acid compound and causes a crosslinking reaction between polyol resin and alkyletherified melamine resin, i.e. they are generally carried out at a temperature of 80.degree..about.180.degree. C. for 20.about.60 minutes. When the baking and drying are carried out under the above condition, the aliphatic sulfonic acid isolated from the aliphatic sulfonic acid compound serves as an acid catalyst to cause the curing of the coated film.
A mixture of 356.0 parts of C.sub.18 H.sub.37 SO.sub.3 Na and 861.4 parts of n-butyl alcohol was charged into a three-necked flask provided with a stirrer, to which was added 98.1 parts of 37% hydrochloric acid at room temperature with stirring to conduct removal of sodium.
The same procedure as in Production Example 1 was repeated by using an aliphatic sulfonate, and inorganic acid and a tertiary amine as shown in the following Table 1 to obtain a solution of aliphatic sulfonic acid compound blocked with equimole of respective tertiary amine and having an effective component concentration (aliphatic sulfonic acid) of 25%. Moreover, 58.5 parts of NaCl in Production Examples 2 and 6.about.8, 71.0 parts of Na.sub.2 SO.sub.4 in Production Example 3 and 85.0 parts of NaNO.sub.3 in Production Examples 4 and 5 were precipitated, respectively, in the removal of sodium.
The same procedure as in Production Example 9 was repeated by using an aliphatic sulfonate, an inorganic acid and an epoxy compound as shown in Table 1 to obtain a solution of aliphatic sulfonic acid compound esterified with equimole of respective epoxy compound and having an effective component concentration (aliphatic sulfonic acid) of 30%. Moreover, 58.5 parts of NaCl and 71.0 parts of Na.sub.2 SO.sub.4 were precipitated in the removal of sodium in Production Examples 10 and 11, respectively.
2  3   4  5   6  7  8  10 11
##STR17##     386.0
##STR18##        400.0
C.sub.18 H.sub.37 OCH.sub.2 CH.sub.2 SO.sub.3 Na
C.sub.18 H.sub.37 (OCH.sub.2 CH.sub.2).sub.2 SO.sub.3 Na
C.sub.8 H.sub.17 SO.sub.3 Na 216
C.sub.12 H.sub.25 SO.sub.3 Na   272
##STR19##                         358
##STR20##                            412.0
##STR21##                               414.0
n-butyl alcohol     951.4
methyl ethyl ketone                        698.4
2  3  4  5   6   7  8  10  11
37.2% hydrochloric acid
98.1         98.1
96.0% sulfuric acid
51.0                    51.0
61.4% nitric acid   102.6
pyridine      79.0
79.0      79.0
N,N--dimethyl benzylamine
135.0     135.0
N,N--dimethyl ethanolamine
89.0       89.0
phenyl glycidyl ether                150.0
Kardula E10                              250.0
mol ratio of aliphatic sulfonate/inorganic acid
mol ratio of aliphatic sulfonate/tertiary amine
mol ratio of aliphatic sulfonate/epoxy compound
Into a four-necked flask provided with a stirrer, a thermometer, a constant water receiver with a reflux condenser and a nitrogen gas inlet was charged a mixture of 190.0 parts of p-toluene sulfonic acid monohydrate and 266.0 parts of xylene. The temperature was raised while blowing nitrogen gas and then the stirring was continued at 140.degree. C. for 2 hours to remove 18 parts of water. After the reaction mass was cooled in air, the nitrogen gas inlet was replaced with a dropping funnel and 250.0 parts of Kardula E10 was added dropwise through the dropping funnel for 30 minutes while stirring at room temperature. After the completion of the dropwise addition, the stirring was continued at room temperature for 4 hours, and the reaction was stopped at an acid value of involatile matter of not more than 1 to obtain an ester solution of p-toluene sulfonic acid esterified with equimole of Kardula E10 and having an effective component concentration (aromatic sulfonic acid) of 25%.
PRODUCTION EXAMPLE 15 (a) Production of Vinyl Type Monomer Containing Polyester Chain Group
A mixture having the following composition was charged into a four-necked flask provided with a stirrer, a reflux condenser, a thermometer and a nitrogen gas inlet, the temperature of which was raised up to 140.degree. C. with stirring.
benzoic acid           122.0  parts
Kardula E10            250.0  parts
phthalic anhydride     148.0  parts
N,N--dimethylbenzylamine
xylene                 327.0  parts
The stirring was continued at a temperature of 140.degree. C. for 2 hours while blowing nitrogen gas to provide an acid value of involatile matter of 108, whereby a reaction intermediate having a carboxyl group in terminal of molecule was obtained. Then, the reaction intermediate was reacted with a mixture of Kardula E10/phthalic anhydride=250.0 parts/148.0 parts under the above reaction condition two times. When the acid value of involatile matter reached 43, the reaction was stopped to obtain a polyester compound solution having a carboxyl group in terminal of molecule with an involatile content of 80%. Then, a mixture containing this polyester compound solution and having the following composition was stirred at a temperature of 140.degree. C. for 4 hours, and the reaction was stopped at an acid value of involatile matter of not more than 1 to obtain a solution of vinyl type monomer containing polyester chain group having an involatile content of 80%.
above polyester compound solution
1,645.0 parts
glycidyl methacrylate   142.0   parts
hydroquinone            2.0     parts
xylene                  35.0    parts
Into a four-necked flask provided with a stirrer, a reflux condenser, a thermometer and a dropping funnel was charged 85.5 parts of xylene, which was heated to 95.degree. C. while raising temperature with stirring. Then, a mixture having the following composition was added at a constant addition speed and a temperature of 95.degree. C. over 2 hours and further held at 95.degree. C. for 2 hours to obtain a dispersion stabilizer solution having an involatile content of 50%.
above vinyl type monomer containing
polyester chain group solution (a)
62.5   parts
butyl methacrylate       50.0   parts
t-butylperoxy-2-ethyl hexanoate
Into a four-necked flask provided with a stirrer, a reflux condenser, a thermometer and a dropping funnel were charged 85.7 parts of the above dispersion stabilizer solution (b) and 57.1 parts of xylene, which was heated to 95.degree. C. while raising temperature with stirring. Then, a mixture having the following composition was added at a constant addition speed and a temperature of 95.degree. C. over 2 hours and further held at 95.degree. C. for 2 hours to obtain an opaque white non-aqueous polymer dispersion having an involatile content of 40%, a viscosity at 20.degree. C. of 0.8 poise and an average particle size of 0.18 .mu.m.
methyl methacrylate     57.9   parts
acrylonitrile           20.0   parts
glycidyl methacrylate   1.4    parts
acrylic acid            0.7    part
xylene                  57.2   parts
mineral spirit          55.2   parts
This dispersion was stable even after being left to stand at 20.degree. C. for one month and exhibited no particle settlement, phase separation and viscosity change.
PRODUCTION EXAMPLES 16-18 (a) Production of Vinyl Type Monomer Containing Polyester Chain Group
Into the same four-necked flask as in Production Example 15(a) was charged a mixture having a composition as shown in the following Table 2, which was heated to 140.degree. C. while raising temperature with stirring. At this temperature, the stirring was continued for 2 hours while introducing nitrogen gas thereinto to thereby obtain reaction intermediate solutions having a carboxyl group in terminal of molecule and acid values of involatile matter of 119 in Production Example 16, 120 in Production Example 17 and 102 in Production Example 18, respectively. then, the above reaction intermediate was reacted with a mixture having a composition as shown in the following Table 3 under the above condition 4 times in Production Example 16, 7 times in Production Example 17 and 5 times in Production Example 18, and the reaction was stopped at acid values of final involatile matter of 27 in Production Example 16, 24 in Production Example 17 and 30 in Production Example 18, respectively, to obtain a polyester compound solution having a carboxyl group in terminal of molecule with an involatile content of 80%. Thereafter, the polyester compound solution was stirred according to a compounding recipe as shown in the following Table 4 at a temperature of 140.degree. C. for 4 hours and the reaction was stopped at an acid value of involatile matter of not more than 1 to obtain a vinyl type monomer containing polyester chain group solution having an involatile content of 80%.
(part)  (part)  (part)
lauric acid           200.0
stearic acid                  284.0
Kardula E10   250.0
phenyl glycidyl ether 150.0   150.0
succinic anhydride    118.0   118.0
xylene        512.0   582.0   469.0
16(a) (part)
17(a) (part)
18(a) (part)
Kardula E10  250.0
phenyl glycidyl ether   150.0     150.0
succinic anhydride      118.0     118.0
2,580.0    2,930.0   2,365.0
142.0      142.0     142.0
hydroquinone 2.0        2.0       2.0
xylene       35.0       35.0      35.0
Into the same four-necked flask as in Production Example 15(b) was charged xylene in an amount of 78.0 parts in Production Example 16, 91.7 parts in Production Example 17 or 85.5 parts in Production Example 18, which was heated to 95.degree. C. while raising temperature with stirring. Then, a mixture having a composition as shown in the following Table 5 was added at a constant addition speed and a temperature of 95.degree. C. over 2 hours and further held at 95.degree. C. for 2 hours to obtain a dispersion stabilizer solution having an involatile content of 50%.
Example Example   Example
16(b) (part)
17(b) (part)
18(b) (part)
vinyl type monomer con-
taining polyester chain
group solution obtained in
Production Example 16(a)
Production Example 17(a)
group solution obtained in         62.5
Production Example 18(a)
butyl methacrylate                 50.0
t-butylperoxy-2-ethyl
hexanoate      2.0       2.0       2.0
The dispersion was stable even after being left to stand at 20.degree. C. for one month and exhibited no particle settlement, phase separation and viscosity change.
Example   Example   Example
16(c)     17(c)     18(c)
(part)    (part)    (part)
solution obtained in
Production Example 16(b)
solution obtained in     85.7
Production Example 17(b)
solution obtained in               85.7
Production Example 18(b)
xylene         15.0      103.7     30.0
mineral spirit 30.0      180.0     27.1
57.9      57.9      57.9
acrylonitrile  20.0      20.0      20.0
2-hydroxyethyl 20.0      20.0      20.0
1.4       1.4       1.4
acrylic acid   0.7       0.7       0.7
xylene         5.0       50.0      57.2
mineral spirit 15.0      50.0      55.2
hexoanate
16(c) (part)
17(c) (part)
18(c) (part)
involatile content (%)
55        25        40
viscosity (20.degree. C.) (poise)
2.5       0.7       0.9
average particle size (.mu.m)
0.16      0.17      0.18
PRODUCTION EXAMPLES 19-23 (a) Production of Vinyl Type Monomer Containing Polyester Chain Group
Into the same four-necked flask as in Production Example 15(a) was charged a mixture having a composition as shown in the following Table 8, which was heated to 140.degree. C. while raising temperature with stirring. The stirring was continued at this temperature for 2 hours while introducing nitrogen gas thereinto to obtain reaction intermediate solutions having a carboxyl group in terminal of molecule, and acid values of involatile matter of 214 in Production Example 19, 257 in Production Example 20, 145 in Production Example 21, 253 in Production Example 22 and 168 in Production Example 23, respectively. Then, the reaction intermediate solution was reacted with a mixture having a composition as shown in the following Table 9 under the same condition 2 times in Production Example 19, 5 times in Production Example 20, 10 times in Production Example 21 and 4 times in Production Examples 22 and 23, and the reaction was stopped at an acid value of final involatile matter of 57 in Production Example 19, 28 in Production Example 20, 20 in Production Example 21, 31 in Production Example 22 or 29 in Production Example 23 to obtain a polyester compound solution having a carboxyl group in terminal of molecule with an involatile content of 80%. The resulting polyester compound solution was stirred according to a compounding recipe as shown in the following Table 10 at a temperature of 140.degree. C. for 4 hours, and the reaction was stopped at an acid value of involatile matter of not more than 1 to obtain a vinyl type monomer containing polyester chain group solution having an involatile content of 80%.
cyclohexyl alcohol 100.0
stearyl alcohol         270.0
n-butyl alcohol              74.0
lauryl alcohol                    186.0
hexahydro-phthalic
anhydride     154.0
succinic anhydride 118.0
phthalic anhydride           148.0
2.0  4.0  6.0  4.0  4.0
xylene        284.0
AOE-X-24(a)    205.0
Kardula E10                   250.0
styrene oxide            120.0
hexahydro-phthalic anhydride
succinic anhydride  118.0
phthalic anhydride            148.0
tion  tion  tion  tion  tion
19(a) 20(a) 21(a) 22(a) 23(a)
polyester compound solution
142.0 142.0 142.0 142.0
hydroquinone  2.0   2.0   2.0   2.0   2.0
xylene        30.0  35.0  35.0  35.0  35.0
Into the same four-necked flask as in Production Example 15(b) was charged xylene in an amount of 88.0 parts in Production Example 19, 73.0 parts in Production Example 20, 93.0 parts in Production Example 21 or 85.5 parts in Production Examples 22 and 23, which was heated to 95.degree. C. while raising temperature with stirring. Then, a mixture having a composition as shown in the following Table 11 was added at a constant addition speed and a temperature of 95.degree. C. over 2 hours and further held at 95.degree. C. for 2 hours to obtain a dispersion stabilizer solution having an involatile content of 50%.
vinyl type monomer
chain group solution in
Production Example 19(a)
Production Example 20(a)
Production Example 21(a)
chain group solution in     62.5
Production Example 22(a)
containing polyester             62.5
Production Example 23(a)
30.0      30.0
butyl methacrylate          50.0 50.0
lauryl methacrylate    50.0
hexanoate    2.0  2.0  2.0  2.0  2.0
The above dispersion was stable even after being left to stand at 20.degree. C. for one month and exhibited no particle settlement, phase separation and viscosity change.
solution of Production
solution of Production 85.7
solution of Production     85.7
xylene     15.0
--  30.0
xylene     10.3
--  57.2
Produc-      Produc-  Prodc-   Produc-
tion         tion     tion     tion   tion
Example      Example  Example  Example
19(c)        20(c)    21(c)    22(c)  23(c)
(part)       (part)   (part)   (part) (part)
55       40       50     40     40
3.2      1.3      2.1    0.8    0.8
average 0.19     0.18     0.15   0.17   0.18
PRODUCTION EXAMPLE 24 (a) Production of Vinyl Type Monomer Containing Polyester Chain Group
Into the same four-necked flask as in Production Example 15(a) was charged a mixture having the following composition, which was heated to 140.degree. C. while raising temperature with stirring:
178.0 parts
Kardula E10         250.0 parts
154.0 parts
xylene              145.0 parts
The polyester compound solution was stirred according to the following compounding recipe at 140.degree. C. for 4 hours and the reaction was stopped at an acid value of involatile matter of not more than 1 to obtain a vinyl type monomer containing polyester chain group solution having an involatile content of 80%:
728.0 parts
glycidyl acrylate     130.0 parts
hydroquinone          1.0 part
xylene                31.0 parts
Into the same four-necked flask as in Production Example 15(b) was charged 83.0 parts of xylene, which was heated to 95.degree. C. while raising temperature with stirring. Then, a mixture having the following composition was added at a constant addition speed and a temperature of 95.degree. C. over 2 hours and further held at 95.degree. C. for 2 hours to obtain a dispersion stabilizer solution having an involatile content of 50%:
methyl methacrylate    20.0 parts
butyl methacrylate     20.0 parts
The same method as in Production Example 15(c) was repeated except that the dispersion stabilizer solution of Production Example 24(b) was used instead of the dispersion stabilizer solution of Production Example 15(b) to obtain an opaque white non-aqueous polymer dispersion having an involatile content of 40%, a viscosity at 20.degree. C. of 1.0 poise and an average particle size of 0.18 .mu.m. This dispersion was stable even after being left to stand at 20.degree. C. for one month and exhibited no particle settlement, phase separation and viscosity change.
PRODUCTION EXAMPLE 25 (a) Production of Vinyl Type Monomer
Into a four-necked flask provided with a stirrer, a thermometer, a quantitative water receiver with a reflux condenser and an inlet for nitrogen gas was charged 1,500 parts of 12-hydroxy stearic acid, which was stirred at 200.degree. C. while raising temperature with stirring and blowing nitrogen gas. After the reaction was stopped at an acid value of 39, the reaction mass was cooled in air and added with 159 parts of xylene to obtain a 5 mole condensate solution of 12-hydroxy stearic acid having an involatile content of 90%. In this case, 72 parts of water was removed. Then, a mixture inclusive of the 5 mole condensate solution of 12-hydroxy stearic acid having the following composition was stirred in a four-necked flask provided with a stirrer, a thermometer, a reflux condenser and an inlet for nitrogen gas at a temperature of 120.degree. C. to conduct an esterification reaction until the acid value of involatile matter was not more than 1.0, whereby a vinyl type monomer solution having an involatile content of 80% was obtained:
5 mole condensate solution
1,586.67 parts
of 12-hydroxy stearic acid
142.00 parts
3.93 parts
hydroquinone       1.96 parts
xylene             227.94 parts
above vinyl type monomer solution
(a)312.50 parts
methyl methacrylate    245.00 parts
methacrylic acid       5.00 parts
Into the same four-necked flask as in Production Example 15(c) were charged 19.50 parts of the above dispersion stabilizer solution (b) and 1,233 parts of mineral spirit, which were warmed to 85.degree. C. with stirring and added with a mixture having the following composition at this temperature and then held at 85.degree. C. for 20 minutes:
64.00 parts
methacrylic acid  1.00 part
3.00 parts
Then, 1.00 part of n-octylmercaptane was added, and thereafter two mixtures (I) and (II) having the following compositions were simultaneously added over 1.5 hours in case of the mixture (I) and over 3 hours in case of the mixture (II) at a temperature of 85.degree. C. and further the temperature of 85.degree. C. was held for 30 minutes to obtain an opaque white non-aqueous polymer dispersion having an involatile content of 555, a viscosity at 20.degree. C. of 1.0 poise and an average particle size of 0.19 .mu.m:
Mixture (I)
above dispersion stabilizer (b)
124.50 parts
mineral spirit      67.00 parts
Mixture (II)
methyl methacrylate 1,400.00 parts
methacrylic acid    28.60 parts
n-octylmercaptane   2.20 parts
The resulting dispersion was stable even after being left to stand at 20.degree. C. for one month and exhibited no particle settlement, phase separation and viscosity change.
COMPARATIVE EXAMPLE 1 (a) Production of Vinyl Type Monomer
benzoic acid       122.0 parts
142.0 parts
xylene             65.3 parts
Into the same four-necked flask as in Production Example 15(b) was charged 85.5 parts of xylene, which was heated to 95.degree. C. while raising temperature with stirring. Then, a mixture having the following composition was added at a constant addition speed and a temperature of 95.degree. C. over 2 hours and further held at 95.degree. C. for 2 hours to obtain a dispersion stabilizer solution having an involatile content of 50%:
butyl methacrylate    50.0 parts
COMPARATIVE EXAMPLE 2 (a) Production of Vinyl Type Monomer Containing Polyester Chain Group
Into the same four-necked flask as in Production Example 15(a) was charged a mixture having the following compositon, which was heated to 140.degree. C. while raising temperature with stirring. The stirring was continued at this temperature for 2 hours while introducing nitrogen gas thereinto to obtain a reaction intermediate solution having an acid value of involatile matter of 108 and a carboxyl group in terminal of molecule.
Kardula E10        250.0 parts
phthalic anhydride 148.0 parts
xylene             1,215.0 parts
The resulting reaction intermediate solution was reacted with a mixture of Kardula E10/phthalic anhydride=250.0 parts/148.0 parts under the same condition 11 times, and then the reaction was stopped at an acid value of final involatile matter of 11 to obtain a polyester compound solution having a carboxyl group in terminal of molecule and an involatile content of 80%. This polyester compound solution was stirred according to the following recipe at a temperature of 140.degree. C. for 4 hours and the reaction was stopped at an acid value of involatile matter of not more than 1 to obtain a vinyl type monomer containing polyester chain group solution having an involatile content of 80%.
6,123.0 parts
hydroquinone         2.0 parts
xylene               35.0 parts
butyl methacrylate     50.0 parts
COMPARATIVE EXAMPLE 3 (a) Production of Dispersion Stabilizer
vinyl type monomer containing
polyester chain group solution
of Production Example 15(a)
butyl methacrylate   90.0 parts
COMPARATIVE EXAMPLE 4 (a) Production of Vinyl Type Monomer Containing Polyester Chain Group
Into the same four-necked flask as in Production Example 15(a) was charged a mixture having the following composition, which was heated to 140.degree. C. while raising temperature with stirring. The stirring was continued at this temperature for 4 hours while introducing nitrogen gas thereinto and the reaction was stopped at an acid value of involatile matter of not more than 1 to obtain a vinyl type monomer containing polyester chain group solution having an involatile content of 80%.
Kardula E10         750.0 parts
phthalic anhydride  444.0 parts
hydroquinone        1.6 parts
xylene              327.4 parts
Into the same four-necked flask as in Production Example 15(b) was charged 85.5 parts of xylene, which was heated to 95.degree. C. while raising temperature with stirring. Then, a mixture having the following composition was added at a constant addition speed and a temperature of 95.degree. C. over 2 hours and further held at 95.degree. C. for 2 hours to obtain a dispersion stabilizer solution having an involatile content of 50%.
polyester group solution (a)
aliphatic sulfonic acid compound solution of
non-aqueous polymer dispersion of
50.0   parts
Production Example 15(c)
polyester resin solution (involatile content: 85%,
82.4   parts
XP-5770-85, made by Kargil Corp.)
methylated melamine resin (involatile content: 100%,
30.0   parts
number-average molecular weight: 370, Cymel 303,
trade name, made by Mitsui Cyanamid Co., Ltd.)
rutile titanium dioxide (Teika Sanka Titan JR-602,
84.0   parts
trade name, made by Teikoku Kako Co., Ltd.)
xylene                     18.0   parts
n-butyl alcohol            2.0    parts
The above ingredients other than the melamine resin were charged into a sand mill and dispersed to a particle size of not more than 10 .mu.m for 30 minutes. Then, the melamine resin was added to produce a coating.
Thereafter, the coating was diluted to a given coating viscosity (Ford Cup No. 4, 20.degree. C., 30 seconds) with a thinner (xylene/n-butyl alcohol=9/1 weight ratio). Then, this diluted coating was sprayed under air pressure to a test panel, wherein a phosphated soft steel panel was electrodeposited with a cathodic electrodeposition coating (Aqua No. 4200, trade name, made by Nippon Oil & Fats Co., Ltd.) at a dry thickness of 20 .mu.m baked at 175.degree. C. for 25 minutes, coated by spraying with a surfacer (Epiko No. 1500cp Sealer, trade name, made by Nippon Oil & Fats Co., Ltd.) at a dry thickness of 40 .mu.m baked at 140.degree. for 30 minutes, and then baked at 140.degree. C. under a vertically stood state for 30 minutes. As a result, when the coated thickness reached up to 45 .mu.m, the sagging was not caused and the bittiness and color change were not observed and consequently a smooth and glossy coated film (specular gloss at 60.degree.:93) was obtained. Further, when a droplet (0.2 ml) of 1N sulfuric acid solution was spotly dropped on this film and left to stand at 20.degree. C. for 4 hours, there was observed no change, and the acid resistance was excellent. Moreover, the film had an excellent water resistance because there was observed no change when the film was immersed in a warm water at 40.degree. C. for 5 days.
2  3  4   5   6  7  8  9  10 11
Aliphatic sulfonic acid
Production Example 5  4.8
Production Example 9      20.0
Production Example 10        18.3
Production Example 11           18.3
Production Example 6               8.0
Production Example 7                  8.0
Production Example 8                     8.0
Production Example 20 175.0
Production Example 21     20.0
Production Example 24        50.0
Production Example 18              25.0
Production Example 22                 25.0
Production Example 23                    25.0
A           85.7      57.1         85.7
B              83.3
C                 100.0      87.5
D                         70.6
Alkyletherified
E           40.0          40.0
F              50.0
G                 20.0             40.0
H                     60.0
I                            31.6
J                               30.0
xylene      25.0
A: Acrydic A413 70S (acrylic resin solution, trade name, made by Dainippo
Ink & Chemicals, Inc., involatile content: 70%)
B: Aroplats 1713R60 (silicon polyester resin solution, trade name, made b
Nisshoku Aro Kagaku Co., Ltd., involatile content: 60%)
C: Joncryl 500 (acrylic resin solution, trade name, made by Johnson Wax
Co., Ltd., involatile content: 80%)
D: Polyester XP5770-85
alkyletherified melamine resin
E: Nikalac MW30 (methylated melamine resin, trade name, made by Sanwa
Chemicals Co., Ltd., involatile content: 100%, numberaverage molecular
weight: 340)
F: Cymel 1130 (methylethyl mixed etherified melamine resin, trade name,
made by Mitsui Cyanamid Co., Ltd., Involatile content: 100%, numberaverag
molecular weight: 460)
G: Cymel 303
H: Cymel 1116 (involatile content: 100%, numberaverage molecular weight:
I: Uvan 120 (butylated melamine resin solution, trade name, made by Mitsu
Toatsu Co., Ltd., involatile content: 95%, numberaverage molecular weight
J: Resimene 755 (methylbutyl mixed etherified melamine resin, trade name,
made by Monsanto Co., involatile content: 100%, numberaverage molecular
weight: 480)
5    6       7      8     9    10
Prorudction  4.0
Prorudction         16.0
Prorudction                 6.7
Prorudction                      0.4
Prorudction                            50.0
Prorudction                                 18.3
Prorudction  50.0   50.0               50.0
Prorudction                      175.0
Prorudction                                 36.4
A                                57.1
C                                           87.5
D            82.4   108.2   82.4       29.4
G            30.0   8.0     30.0       75.0
H                                60.0
J                                           30.0
84.0   84.0    70.0 119.0 84.0 84.0
xylene       18.0   18.0    18.0 32.0  20.0 18.0
2.0    2.0     2.0  3.0   2.5  2.0
1     2       3     4     5     6
Aliphatic sulfonic acid compound
addition amount (a)
Non-aqueous polymer dispersion
addition amount (b)
Polyol resin    Polyester
Acrydic Aroplats    Acrydic
XP-5770-85
A-413-70S
1713-R60
Nikalac MW30
bittiness (1)   good  good    good  good  good  good
good  good    good  good  good  good
glossiness at 60.degree.
93    92      93    91    92    92
sagging limit   45    47      42    49    48    44
thickness (.mu.m) (5)
Polyol resin                    Acrydic Acrydic Acrydic
Alkyletherified melanime resin
U-van 120
bittiness (1)   good    good    good    good    good
93      93      91      92      92
sagging limit   46      45      44      46      45
5      6     7      8     9      10
--     Procution
Example 15   Example 20
20.0 parts   70.0 parts
92.0 parts
bittiness (1)   poor   good  poor   coated film
good   poor  good   was not
92     93    91     cured 92     35
good   good  good         poor   --
good   poor  good         poor   --
sagging limit   44     44    30           46     --
(1) Judgement of bittiness
good: no observation
poor: more than 5/cm.sup.2 was observed on the film surface.
(2) Judgement of color change
poor: considerably observed by visual test
(3) Judgement of acid resistance
(4) Judgement of water resistance
good: blister of film surface was not observed.
poor: blister of more than 10/cm.sup.2 was observed on the film surface.
(5) Evaluation of sagging limit thickness (.mu.m)
The coating diluted to 30 seconds (20.degree. C.) through Ford Cup No. 4
was applied by air spraying to the same test panel as in Example 1 at the
vertically stood state and baked at 140.degree. C. for 30 minutes. Then,
the limit thickness observing no sagging was measured visually.
(a) amount of aliphatic or aromatic sulfonic acid in aliphatic or aromati
sulfonic acid compound based on 100 parts by weight of resin (parts by
(b) amount of polymer solid content in nonaqueous polymer dispersion base
on 100 parts by weight of resin (parts by weight)
Ex-                    esterification agent
am-  Aliphatic                     addition
ple  sulfonic acid     Kind        amount(a)
1    C.sub.18 H.sub.37 SO.sub.3 H
pyridine    1.0
##STR23##        pyridine    0.5
##STR24##        pyridine    1.0
4    C.sub.18 H.sub.37 OCH.sub.2 CH.sub.2 SO.sub.3 H
N,Ndimethyl 1.0
5    C.sub.18 H.sub.37 (OCH.sub.2 CH.sub.2).sub.2 SO.sub.3 H
N,Ndimethyl 1.2
##STR25##        Kardula E10 6.0
##STR26##        phenyl glycidylether
##STR27##        Kardula E10 5.5
9    C.sub.8 H.sub.17 SO.sub.3 H
pyridine    2.0
10   C.sub.12 H.sub.25 SO.sub.3 H
N,Ndiemtyl  2.0
##STR28##        N,Ndimethyl ethanolamine
(a)amount of aliphatic or aromatic sulfonic acid in aliphatic or aromatic
acid  phthalic
ing vinyl    444 parts
type                                         462 parts
mono- Kardula Kardula pheny   pheny   AOE-X-24
E10     E10     glycidyl-
epoxy 750 parts
ehter   ehter
chain  compound              1200 parts
group  mono- benzoic propionic
lauric  stearic --
acid    acid    acid    acid
acid  122 parts
mono- --      --      --      --      benzyl
valent                                alcohol
alcohol                               108 parts
3       5       8       6       2
esterifi-
20         21      22        23
acid  succinic anhydride
708 parts 1298 parts
592 parts 592 parts
ing vinyl
mono  p-t-butyl styrene oxide
Kardula E10
type   functional
epoxy glycidyl-
polyester    1170 parts
chain  mono- --        --       --        --
group  carboxylic
mono- cyclohexyl alcohol
stearyl  n-butyl   lauryl
100 parts alcohol  alcohol   alcohol
alcohol         270 parts
74 parts  186 parts
acrylate  acrylate acrylate  acrylate
142 parts 142 parts
5         10       4         4
--     --     50 parts
--     20 parts
--     --     30 parts
2-ethyl   --     --     75 parts
--     --     --     --     30 parts
40     55     25     40     55
dispersion stabilizer/
30/70  45/55  30/70  30/70  20/80
particle (weight ratio)
state            good   good   good   good   good
viscosity (20.degree. C., poise)
0.8    2.5    0.7    0.9    3.2
0.18   0.16   0.17   0.18   0.19
20      21     22      23
polyester chain group
--      --     50 parts
--      30 parts
2-ethyl        --      --     --      --
--      50 parts
butyl acrylate --      --     --      --
40      50     40      40
dispersion stabilizer/particle (weight ratio)
35/65   70/30  30/70   30/70
state                 good    good   good    good
1.3     2.1    0.8     0.8
0.18    0.15   0.17    0.18
24     1      2      3      4
--     phthalic
constituting    phthalic      anhydride
vinyl type      anhydride     1776 parts
monomer         154 parts
--     Kardula E10
250 parts     3000 parts
p-t-butyl
acid     benzoic acid
monomer  acrylate
1      0      12     3      3
of esterifi-
cation reaction
24     1       2      3       4
butyl meth-
--     --      --     --      --
lauryl meth-
40     40      40     40      40
30/70  30/70   30/70  30/70   30/70
state         good   particle
1.0    --      --     --      --
0.18   --      --     --      --
As shown in Table 16, in Examples 1.about.11, the aliphatic sulfonic acid compound having the structure shown in Table 17, the non-aqueous polymer dispersion having the composition shown in Table 18 and good state, the polyol resin and the alkyletherified melamine resin were used in proper amounts, so that the coated films having a thick sagging limit thickness and no bittiness and color change were obtained and also the acid resistance and water resistance were excellent.
On the other hand, in Comparative Examples 1.about.4, the non-aqueous polymer dispersion could not stably be produced from reasons as mentioned later, so that the desirable coating was not obtained. That is, in Comparative Example 1, the repeated number of esterification reaction in the vinyl type monomer containing polyester chain group as a component for dispersion stabilizer was less than 1, so that the dispersion stability of the non-aqueous polymer dispersion was insufficient and the particles were agglomerated. In Comparative Example 2, the repeated number of esterification reaction exceeded 10, so that the copolymerizability of the vinyl type monomer containing polyester chain group lowered and the molecular weight distribution of the dispersion stabilizer became wider and consequently the dispersion stability of the non-aqueous polymer dispersion was insufficient and the particles were settled. In Comparative Example 3, the amount of vinyl type monomer containing polyester chain group as a component for dispersion stabilizer was less than 20% by weight, so that the particles were agglomerated. In Comparative Example 4, the polyester chain group in the dispersion stabilizer was not arranged near to the main chain but arranged near the terminal of polyester chain group as a side chain, so that the side chain was apt to be entangled with the main chain and the side chain of the dispersion stabilizer was hardly solvated and consequently the dispersion stability of the non-aqueous polymer dispersion was insufficient and the particles were agglomerated.
In Comparative Example 5, the aromatic sulfonic acid compound blocked with pyridine was used instead of aliphatic sulfonic acid compound as an acid catalyst, so that the aromatic sulfonic acid compound precipitated through crystallization in the coating and consequently a large amount of bittiness occurred in the coated film. In Comparative Example 6, since a large amount of the aromatic sulfonic acid compound esterified with the epoxy compound was used instead of the aliphatic sulfonic acid compound, the coated film considerably changed into yellow in the heating and drying. Further, since the resin mixture consisted of more than 90 parts of polyol resin and less than 10 parts of alkyl-etherified melamine resin as solid content, a large amount of blister produced in the coated film after the water resistance test. In Comparative Example 7, the compound of lower aliphatic sulfonic acid having a carbon number of less than 4 blocked with pyridine was used, so that the lower aliphatic sulfonic acid compound precipitated through crystallization in the coating and consequently a large amount of bittiness was observed on the coated surface. Further, the non-aqueous polymer dispersion was not included in the coating, so that the sagging limit thickness was only 30 .mu.m.
1. A higher solid coating composition, comprising 100 parts by weight of a solid resin mixture comprising 30 to 90 parts by weight of a polyol resin and 10 to 70 parts by weight of an alkyletherified melamine resin, 0.2 to 10 parts by weight as an aliphatic sulfonic acid of an aliphatic sulfonic acid compound having a carbon number of 4 to 22, and 1 to 100 parts by weight as a polymer solid content of a non-aqueous polymer dispersion, said non-aqueous polymer dispersion consisting essentially of (a) 40 to 80% by weight of an organic solvent component, (b) 10 to 505 by weight of particle component insoluble in said component (a), and (c) 5 to 40% by weight of a dispersion stabilizer component soluble in said component (a) and capabale of stably dispersing said component (b) into said component (a), said dispersion stabilizer component comprising a product obtained by polymerizing 20 to 100% by weight of a vinyl type monomer containing a polyester chain group represented by the following formula with 0 to 80% by weight of a second vinyl type monomer: ##STR29## wherein X is a hydrogen atom or a methyl group, Y is ##STR30## m and n are from 1 to 10, R.sub.1 is a residue of acid anhydride having a carbon number of 2 to 6, R.sub.2 is a phenyl group, an alkyl or aromatic group having a carbon number of 5 to 19, ##STR31## group (R.sub.5 is an alkyl or aromatic group having a carbon number of 3 to 17, or --CH.sub.2 --O--R.sub.6 group (R.sub.6 is an alkyl or aromatic group having a carbon number of 4 to 18, R.sub.3 is an alkyl group or a residue of aromatic monocarboxylic acid having a carbon number of 1 to 20, and R.sub.4 is a residue of saturated aliphatic, alicyclic or aromatic monovalent alcohol having a carbon number of 1 to 18.
4291137 September 22, 1981 Nakate et al.
4340511 July 20, 1982 Backhouse et al.
4413084 November 1, 1983 Horvath
4525499 June 25, 1985 Hayashi et al.
4611028 September 9, 1986 Peng et al.
0075284 June 1975 JPX
Patent number: 4879337
Inventors: Kishio Shibato (Kamakura), Masataka Kawamura (Fujisawa)
Application Number: 7/115,868
Current U.S. Class: Solid Graft Or Solid Graft-type Copolymer With Other Solid Polymer, Sicp, Or Spfi (524/504); With Solid Polymer Derived From At Least One -n=c=x (x Is Chalcogen) Reactant Wherein At Least One Of The Reactants Forming The Solid Polymer Is Saturated; Or With Spfi Or Sicp Derived From A -n=c=x Reactant Wherein At Least One Of The Necessary Reactants Is Saturated (524/507); With Solid Polymer Derived From At Least One Reactant Wherein At Least One Of The Reactants Forming The Solid Polymer Is An Aldehyde Or Derivative; Or With Spfi Or Sicp Derived From An Aldehyde Or Derivative Wherein At Least One Of The Necessary Reactants Is Saturated (524/512); With Saturated 1,2-epoxy Reactant Containing More Than One 1,2-epoxy Group Per Mole Or Polymer Derived Therefrom; Or With Solid Copolymer Derived From At Least One Unsaturated 1,2-epoxy Reactant Wherein The Epoxy Reactant Contains More Than One 1,2-epoxy Group Per Mole And At Least One Saturated Reactant (525/65); With Solid Polymer Derived From At Least One Nitrogen-containing Reactant Wherein At Least One Of The Reactants Forming The Solid Polymer Is Saturated; Or With Spfi Wherein At Least One Of The Necessary Ingredients Contains A Nitrogen Atom Or With A Reaction Product Thereof; Or With Nitrogen-containing Sicp (525/66); Contacting Two Or More Solid Polymers Derived From Ethylenic Reactants Only With A Poly 1,2-epoxy-containing Reactant; Or Contacting A Solid Polymer Derived From Ethylenic Reactants Only With A Poly 1,2-epoxy-containing Reactant And Subsequently Contacting With An Additional Polymer Derived From Ethylenic Reactants Only (525/108); With Reactant Which Is An Aldehyde, Aldehyde Derivative, Or Polymer Thereof, And Which Is Free Of An 1,2-epoxy Group (included Herein Are Alkylated Methylol Groups) (525/110); Contacting Two Or More Solid Polymers Derived From Ethylenic Reactants Only With A -n=c=x Reactant Or Polymer Thereof; Or Contacting A Polymer Derived From An Ethylenic Reactant Only With A -n=c=x Reactant Or Polymer Thereof And Subsequently Adding Thereto A Solid Polymer Derived Only From Ethylenic Reactants (525/125); Contacting With A -n=c=x-containing Reactant Which Has Been Previously Reacted With An Organic Compound Containing A Hydroxyl, Amine, Or -c(=o)-o- Group (525/127); Contacting Two Or More Solid Polymers Derived From Ethylenic Reactants Only With An Aldehyde Or Aldehyde-type Reactant; Or Contacting A Polymer Derived From Ethylenic Reactant And Subsequently Contacting With A Solid Polymer Derived From Ethylenic Reactants Only (525/155); Solid Polymer Derived From Ethylenic Reactants Only Derived From Reactant Containing A Heterocyclic Ring Or Fused-, Bridged-ring System Excluding An Anhydride Group Which Produces The Fused- Or Bridged-ring System Or Heterocyclic Ring (525/161); Solid Polymer Derived From Ethylenic Reactant Only Derived From Reactant Containing Hydroxyl Or Ether Group (525/162)
International Classification: C08F26504; C08L 5108; C08L 6128;