JPS58122970A - Reduction of volatile organic exhaust from polyester composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to reducing volatile organic emissions from polyester compositions. More specifically, the present invention relates to water as a solvent in high solids content polyester coating compositions to reduce organic emissions.

Environmental considerations have become increasingly important in recent years.

This consideration extends not only to environmental conservation itself, but also to public safety regarding living and working conditions. Volatile organic emissions resulting from coating compositions applied and used by industry and the consumer public are often not only unpleasant but also contribute to photochemical smog. The government has designated volatile organic compounds (VOCs) that can be released into the atmosphere.
may establish or are in the process of establishing regulations that set guidelines regarding such matters. United States Environmental Protection Agency (EPA)
) has established guidelines for the amount of VOCs released into the atmosphere, which are planned for adoption by each state in the United States. VOC guidelines and environmental considerations, such as the EPA's guidelines, are particularly relevant to the paint and coating industries that use organic solvents that emit into the atmosphere.

Regarding coating formulations and in response to environmental considerations, organic resins with high solids content have been developed and are known to reduce organic emis- sions when using resin coatings. The higher the solids content, the less solvent is involved in emissions to the atmosphere. Increasing the solids content is almost always a final solution, but generally
Some solvent is required to apply the coating resin. One object of the present invention is to provide a solvent system that is compatible with high solids content polyester coating compositions for baking applications that reduce organic emissions to the atmosphere.

Water with one or more cross-linking agents that can be mixed thoroughly in water and mixed with such polyester/solvent/water combinations from about 5% by weight in water at 25°C. It has been discovered that using (9) as a co-solvent reduces emissions of volatile organic compounds over that experienced when using non-organic solvents.

Chill was discovered to have an affinity for water.

In polyester baking, the amount of water that can be added to the system increases as the hydroxyl value increases and the molecular weight decreases. Accordingly, in the present invention, the amount of water used is determined by the coating and the high solids content polyester may be prepared from the reaction of a tribasic acid with an organic polyol having at least two hydroxyl groups. The resulting high solids content polyester can be mixed with an organic solvent, water, and an amino resin crosslinker with a water solubility ranging from about 5% by weight to fully miscible in water to create a coating composition with reduced volatile organic emissions. You can make things form. vOC
To be effective at reducing water, water should comprise at least about 2% by weight of the coating composition (10) and organic solvents should comprise about 30% by weight of the coating composition.
The preferred range of water to organic solvent is from about 20/80 to about 60/40.

Cellosolve acetate 1- or 2-functional toxyethyl acetate 1-, normal butanol, isobutanol, n
-Propoxypropanol and butyl cellosolve or 2-butoquinoethanol are typical solvents that may be used in the coating composition, with butyl cellosolve being the preferred solvent.

Methylated melamine, methylated urea, and hexamethine methyl melamine are typical amine resin cross-linking agents, commercially available as Cymel 303 from American Anamide Co. Hexamethine methyl melamine is the preferred cross-linking agent. It is a drug.

The present invention is not suitable for cross-linking agents such as urethanes that react with water.

The polyester/solvent/water compositions of the present invention may be kneaded by mechanical mixing of the components. Preferably, the polyester has sufficient organic solubility (11) to reduce its viscosity to Z6 or lower when it is made. Preferably, a cross-linking agent such as Cymel 303 is then added to such polyester organic solvent mixture. Preferably, the remaining desired organic solvent is then added, followed by the desired water. Adding too much water before adding enough organic solvent may result in poor mixing. Preferably, all of the foregoing mixing takes place between room temperature and about 50°C.

High solids content polyesters Preferred polyesters for use with water and organic cosolvents have hydroxyl numbers of at least about 150 to about 350 and number average molecular weights of about 300 to about 1100. Generally they are reacted with dibasic acids or acid anhydrides such as isophthalic acid, adipic acid, phthalic anhydride and terephthalic acid and polyols such as propylene glycol, neopentyl glycol and trimethylolpropane. I
-) Q is coming. Optionally, solvents of the type specified in this invention may be added during or immediately after resin formation for ease of resin handling. Additionally, pigments may optionally be added to the polyester resin. These pigments include metal oxides such as titanium dioxide and iron oxide, metal flakes such as brass or nickel flakes, metal powders, phthalocyanine pigments, monastral (rn, ona
stral) pigments, molybdate pigments such as molybdenum orange, quinacridone pigments, sulfate pigments, carbonate pigments, carbon black pigments, /lica pigments, and other organic and inorganic pigments known in the art. The pigment to binder power ratio is typically about O (for clear coatings) to about 2:1. The solids content of the resulting polyester resin typically ranges from about 85% to about 100% by weight.

Although the polyester examples are provided to illustrate polyesters that can be used in the present invention, they are not intended to limit the scope of the invention.

Example I 41, OOg of propylene glycol, 2982q of fucuric anhydride, and 29.409 +7'l adipic acid (
13) was loaded into the reactor and heated to about 2:38℃ (460℃) under inert gas.
'F) for about 2 hours. After 2 hours, the reaction mixture is cooled to 121"C (250°F) and 1000 Zo of Cellosolve Acetate-1. Hydroxyl value, approximately Z
Viscosities ranging from 3 to about Z5, and gallons (3,78
A polyester having a weight of approximately 98 bonds (44 Kg) per #) is obtained.

Example■ 44.90@ neopentyl glycol (90% in water
), 5779 trimethylolpropane, 23.39g
of adipic acid, and 26.58!17 of isophthalic acid are charged to the reactor and heated slowly to 238°C (460°F) under inert gas until an acid number of no greater than about 1O is reached. Cool the reaction mixture to 250°F and add 15.00 g of cellosolve acetate to the reaction mixture.

The resulting mixture has a number average molecular weight of about 750, a solids content of about 85 polyphenolics, a hydroxyl value of about 175, and a range from about Z4 to about Z6F.
I viscosity, and 42 to 9 (9,3 bond) (14) of 3.781! It is a polyester with a weight per gallon.

Example 47,069σ) propylene glycol, 2896 degrees of adipic acid, 32.969 degrees of inphthalic acid, hydrated monobutyltin oxide, Fascatl-4100, 0059, a product of M&T Chemical Company, were slowly added. 19
to 3°C (380°F) then to 215°C (420°F);
The resin is clear and has an acid value of about 9 (cellosolve acetate-1, 9 in
0%). The reaction mixture was heated to 135°C (
275°F) and add 5 g of cellosolve acetate. The resulting mixture has a number average molecular weight of about 450, a solids content of about 90, a hydroxyl number of about 240 to about 250, a viscosity of about Z5 to about Z6, and a viscosity of about 4.4 Kg (9
8 Bond) 3.781! Weight per (] gallon),
Polyester teal with.

Example 1v The high solids content baking alkyd used in the present invention was mixed with 400 g of soy acid.
), (15) 193! A reactor was charged with trimethylolpropane, 209 g of trimethylol, 6 g of triphenyl phosphate, and 490 g of propylene glycol, and the reactants were heated to about 93°G.
(200°F). 74
89 degrees of isophthalic acid and 100 degrees of terephthalic acid are then added to the reaction mixture and slowly heated to /150 degrees Fahrenheit for about 15 hours until the mixture is clear and the acid number reaches IOK from about 9. The mixture is then heated to about 240°F (116°C).
) and add 3259 Habutil Tenrosolve to the resulting algide resin. The resin has a number average molecular weight of approximately 750, approximately 4.0 Kg (8.95 lbs.)
per gallon), a hydroxyl value of about 150, and a viscosity of about Z2 ('85% in cellosolve acetate). "In the second formulation, tall oil acid (tal) was used instead of soybean acid.
A suitable alkyd may also be obtained by replacing (l oil acid).

Finally, polyesters suitable for use in the present invention may be obtained by mixing the reactants in the proportions shown in Table 1 according to the general procedure of Example I, except that the experiments Approximately 215' from F)
It may be carried out at 420° F. and a fascut is used in all experiments.

Table 1 Polyesters suitable for use in the present invention] 3.0 0.32 3:
U 10:U 2.703 4 2.85 0,15 1,
05 3.0 1.
06 3.3 1.
07 33 8 2.85 0.15921 old (17) 2 1.0 310
9.2 Z54 1.0
224 7.5 Z45
1.0 211 7.9
Z46],,0
262 9.6 Z57 ], 0 1.
0 262 8.6 Z58
1.0 10 224 7.
3 Z39 1.0 0.9
243 7.9 Z3 Co-Solvent Polyester Amino Resin Formulation According to the present invention, the aforementioned high solids polyesters contain up to about 30 wt. Solvents or solvent mixtures, at least twice as much water, based on the weight of the coating composition, and one or more cross-linked resins that can be mixed with such polyester/solvent/water combinations. That's fine.

(+8) This polynylsol/solvent/water combination forms a coating composition with reduced emissions of conventional volatile organic formulations compared to the use of neat organic solvents. Preferred cross-linking agents are methylated melamine, methylated urea,
Alternatively, hexamethine methylmelamine, which forms about 20 to about 35 parts of the coating composition.

Table 1 describes various formulations that provide VOC reduction by using water as a solvent in the coating composition. Table 2 also shows the amount of solids (NV) and volatile organic compounds per 1000 g of coating composition for systems using Celon Lube Acetate (CA) as solvent, butyl cellosolve (BC) as solvent and butyl cellosolve-aqueous solvent. It also includes the amount of. In each case, a polyester or alkyd resin was combined with hexamethoxymethylmelamine, commercially known as Cymel 303 (Cy303).

Part ■ Reduction of vOC using surface water tank co-solvent (I9) Resin 0Hliffi Resin/(J303
VOC solvent Example 11 175 75/25
2B-CA Example 1 [17575/25 3O-
BC Example H17575/25 24.0-Be resin 4, Table 1 220 73/27 25-CA resin 4, Table 1 220 73/27 27-Be resin 4, Table 1 220 73/27 19.3 -B
C Example 1 245 70'/30 23-
CA example layer 24.5 70/30 25
-BC Example Example 245 70/30 1
2.0-Be resin 6, Table 1 260 73/27
22-CA resin 6, Table 1 260 73/27
24-Be resin 6, Table 1 260 73/27
""'4-BC Resin 1, Table 1 320 70/30 2O-CA
Resin 11 Table 1 320 70/30 2l-BC
(20) Resin OH value Resin/Cp 303 VOC solvent Example IV 150 75/25. 3O-
CA Example IV 150 75/25 31
．． 5-BC Actual MfHV 150 75/25
25.8-Be resin 6, Table 1 260 73/2
7 13.7-Be resin 6, Table 1 260 70
/30 8.3-Be Resin Water% ChiNV Stomach 3
09 Example 11 - 72 480 Example 1
- 80 (524) Example U
8.0 68 440 Resin 4, Table 1 -
754,30 Resin 4, Table 1 -73 (468) Resin 4, Table 1 9.9 70.8 373
Example Seal -'17 404 Example 1
, - 75 (440) Implementation inversion 1
2.0? 5.7 250 (21) Resin Water % Nv VOC (c/10009 (film) Resin 6, Table 1 -78375 Resin 6, Table 1 -76 (410) Resin 6, Table 1 10.0 73 322 Resin 1, Table 1 -80351 Resin 1, Table 1 -78 (387) Resin 11 Table 1 13.7 76 228 Example IV 70 524 Example IV
68.5 (557) Example IV
6.7 67.5 475 Resin 6, 1st
Table 9.2 77 263 Resin 1, Table 1
11.5 80 193H20-B(J:tc
A Resin VOC reduction Example ■ Example H Example ■ 8.3% resin 4,
Table 1 (22) Resin 4, Table 1 Resin 4, Table 1 132% Example Seal Implementation Inverted Example 1 381% Resin 6, 1st
Table Resin 6, Table 1 *Resin 6, Table 1 141% Resin 1, Table 1 Resin 1, Table 1 *Resin 1, Table 1 350% Example ■ Example ■ Example IV 9.3% resin 6
, Table 1 299% resin 1, 1st
Table 450% (23) *Can increase if all are BC.

() Because it is not used in the calculation of "VOC reduction chi".

BC series are shown in parentheses.

Table 1 shows formulations of various high solids polyesters and alkyds with Cymel 303 and various organic solvent-water combinations.

Table Polyester/Synul 303/Solvent based resin O
H-valent resin/C7303VOC solvent example device 24
5 70/30 23-CA Example 245
70/30 18.4-CA2.8-CA.

Example layer 245 70/30 □. -Bc Example 1 245 70/30 3.0-CA.

8-n-BuOH Example 1 245 70/30 12.0-B
C Example 1 175 75/25 28-CA
Example 1 [17575/25 24.5-CA Example 1 175 75/25 24.0-BC Example 1 160 75/25 18.7-CA (
24) Resin OH value Resin/Ct7303 VOC solvent resin 4, Table 1 220 73/27 2O-
CA resin 4, Table 1 220 73/27 19.
3-BC resin 6, Table 1 260 73/27 1
8-CA resin 6, Table 1 260 73/27 3
CA・4-BC Resin 1, Table 1 320 70/30 l8-C
A resin 1, Table 1 320 70/30 2・7-
CA.

7.6-BC Example IV 150 75/25 3O-C
A Example IV 150 75/25 31.
5-BC Example ■150 75/25 25.8-
BC Example drawing -77404 Example seal 4.6 77 337 Examples 10.7 76.5 260 Examples
11.0 78 233 Example Seal 12.0
75.7 250 Example II-72
480 (25) Example 1 3.5 72 430 Example 1
8.0 68 440 Examples (6,07
5355 Resin 4, Table 1 6.0 75 378 Resin 4, Table 1 9.9 70.8 373 Resin 6
, Table 1 6.0 75 348 Resin 6, Table 1 10.0 73 322 Resin 11 Table 1 9.0 75 333 Resin 1, Table 1 13
．． 7 76 228 Example IV-70
524 Example IV -68,5557 Example IV
6.7 67.5 475 The hydroxyl value, polyester cross-linking agent ratio, water content, solid content, and ■OC grams for each formulation are all shown in the table below.
1 shows the general reduction in OC with water/organic/solvent combinations.

(26) The amount of water that can be added to polyester and amine resin crosslinkers is closely related to the hydroxyl content of the polyester or alkyd. Under conditions of maximum water solubility in the case of low level melamine with butyl cellosolve as the sole co-solvent, the hydroxyl value is the number of bonds of water that can be added to 1000 pounds (45(1;')) of the polyester portion of the system formulation. approximately equal to.

In general, water tolerance decreases with increasing content of amine resin cross-linker or when poly(haserosolve acetate) is present in the system.

However, in general, the resin, solvent, and cross-linking agent are (OH value.) (X□) + (OH value 8) (X8) + (OH value.
Value. )(Xc) 105 where the OH value □, 3. . represents the hydroxyl value of the resin, solvent, and cross-linking agent, XJS. each represents the proportion by weight of the components, and XR + XS + The scope of the invention should therefore be defined by the appended claims and their equivalents.

Patent applicant: Cargill Incorporated (28
) Procedures Tadashi Sode Written on February 2, 1982, Title of the invention: Method for reducing volatile organic emissions from polyester compositions 3, Relationship with the case of the person making the amendment Patent applicant's address Name: Cargill Co., Ltd. Incorporated 4 agent 6, l'-(OH value C) (XC
)105J is corrected as [”(OH value C)(Xc)>105j.

that's all

Claims (1)

[Claims] 1. A polyester having a hydroxyl value of at least about 150;
An organic solvent with water solubility ranging from about 5-fold to complete miscibility in water; at least about 2% by weight of the coating solution.
water; and a polyester as described above, an organic solvent, and a cross-linking agent that is miscible with water. 2. The coating solution according to claim 1, wherein the cross-linking agent is an amine resin. 3. The coating solution according to claim 1, wherein the coating solution further contains a pigment. 4. The organic solvent is cellosolve acetate, butyl cellosolve, n-butyl alcohol, isobutanol, n-
selected from the group consisting of propoxypropanol and mixtures thereof; Claim No. 2.18.19.20
or the coating solution according to item 21. 2. The coating solution of claim 2, wherein the amine resin cross-linking agent of 5-1- is selected from the group consisting of methylated melamine, hexamethoxymethyl melamine, methylated urea, and mixtures thereof. 6. Claim No. 5.18.19.2, wherein the water to organic solvent is in a ratio ranging from about 20/80 to about 60/40.
22. The coating solution according to item 0 or 21. 7. A method for reducing volatile organic emissions from a polyester coating solution, comprising: a polyester having a hydroxyl value of at least about 150; , an organic solvent present in an amount less than about 30% by weight of the coating solution; and a cross-linking agent that is miscible with the polyester, the organic solvent, and water; A method consisting of admixing water in an amount of at least 2% by weight. 8. The method of claim 7, wherein the cross-linking agent is an h''-amino resin. 9. The method of claim 7, wherein the polyester comprises a pigment. 10. The organic solvent. Claim 8.22. is selected from the group consisting of cellosolve acetate, butylcerone 7'', n-butyl alcohol, isobutanol, n-propoxypropanol, and mixtures thereof.
23. The method according to paragraph 24 or 25. 11. The amine resin cross-linking agent is methylated melamine,
9. The method of claim 8, wherein the melamine is selected from the group consisting of hexamethoxymethylmelamine, methylated urea, and mixtures thereof. 12 Water to organic solvent is about 20/80 to about 6074
12. The method of claim 11, wherein the ratio is in the range of zero. 13 Reacting an organic dibasic acid or acid anhydride with a 4-hydroxyl organic polyol containing at least two hydroxyl groups to form a polyester having a hydroxyl value of at least 150; and a coating solution made by mixing the polyester, the organic solvent, and the water-miscible cross-linking agent, wherein the organic solvent ranges from about 5% by weight to complete admixture in water. and is present in an amount less than about 30% by weight of the coating composition, and wherein the water is at least about 2% by weight of the coating composition. 14. The coating solution of claim 13, wherein the cross-linking agent is an amine resin. 15. The coating solution according to claim 13, wherein the organic solvent is selected from the group consisting of cellosolve acetate, butyl cellosolve, -butyl alcohol, isobutanol, n-propoxypropanol, and mixtures thereof. . 16. The coating solution of claim 14, wherein the amino resin crosslinker is selected from the group consisting of methylated melamine, hexamethine methylmelamine, methylated urea, and mixtures thereof. 17 Water to organic solvent is about 20/80 to about 60/4
17. A coating solution according to claim 16, wherein the coating solution is present in a ratio in the range of 0. 18 Polyesters having hydroxyl values ranging from about 1'50 to about 350 and number average molecular weights ranging from about 300 to about 1100; organic solvents having water solubility ranging from about 5% by weight to complete miscibility in water; A coating solution comprising at least about 2% water by weight of the coating solution; and a cross-linking agent that is miscible with the polyester, organic solvent, and water described above. 19 The above polyester is a reaction product of a dibasic acid or its acid anhydride and a polyol. Coating solution according to claim 18. 20. The tribasic acid or anhydride thereof is selected from the group consisting of inphthalic acid, adipic acid, phthalic acid, terephthalic acid, anhydrides thereof, and mixtures thereof, and the polyol is propylene glycol, neopentyl glycol, Coating solution according to claim 19, selected from the group consisting of trimethylolpropane, and mixtures thereof. 21. The coating solution of claim 19, wherein the cross-linking agent is an amino resin selected from the group consisting of methylated melamine, hexamethoxymethylmelamine, methylated urea, and mixtures thereof. 22, hydroxyl value ranging from about 150 to about 350 and about 30
A polyester having a number average molecular weight ranging from 0 to about 1100; an organic solvent having a water solubility ranging from about 5% by weight to complete admixture in water and in an amount less than about 30% by weight of the coating solution; and a polyester, an organic solvent and a water-miscible cross-linking agent;
A method of reducing volatile organic emissions from a polyester coating solution comprising mixing a heavy quantity of water. 23. The method of claim 22, wherein the polyester is a reaction product of a tribasic acid or anhydride thereof and a polyol. 24 The tribasic acid or anhydride thereof is selected from the group consisting of isophthalic acid, adipic acid, phthalic acid, and terephthalic acid, anhydrides thereof, and mixtures thereof, and the polyol is selected from the group consisting of isophthalic acid, adipic acid, phthalic acid, and terephthalic acid, anhydrides thereof, and mixtures thereof, and the polyol is selected from globylene glycol, neopentyl 24. The method of claim 23, selected from the group consisting of glycols, trimethylolpropane and mixtures thereof. 25. The method of claim 23 or 24, wherein the cross-linking agent is an amine resin selected from the group consisting of methylated melamine, hexamethoxymethylmelamine, methylated urea, and mixtures thereof. .