NZ202684A - Herbicidal spray compositions comprising glycol ether solvent(s) - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £02684 t *- J. P. & s. ,0U< . 2026 8 4 Priority Dst6(s)T Complete Specification Filed: ^ Class: .ftQW.§Sj.Q& Publication Date: .... jy.DEe.i P.O. Journal, No: .ms ■i luniu NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION HERBICIDAL COMPOSITIONS X/We, THE DOW CHEMICAL COMPANY, 2 030 Dow -Ccntva, Abbott Road, Midland, Michigan 48640, United States of America, a corporation organized and existing under the laws of the State of Delaware, United States of America hereby declare the invention for which £ / we pray that a patent may be granted to j4k/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- - 1 - (followed by la) 202684- - la - HERBICIDAL COMPOSITIONS The present invention provides a herbicidal spray composition comprising: (a) an effective amount of at least one brush controlling herbicide; (b) from 0.1 to 60 percent by volume of a glycol ether of the formula R-0-(CH„-CH0) H (I) 2 n wherein R represents alkyl or phenyl, each independently represents hydrogen, methyl or ethyl, and n represents the integers 1 to 10, inclusive; (c) from 20 to 98 percent by volume water, and optionally (d) up to 20 percent by volume of one or more acceptable surfactants and (e) up to 2 5 percent by volume petroleum distillate oil.

The present invention also provides an improved method for the kill and control of undesired brush and other woody vegetation in which the herbicidal spray composition of -2- .< x) y *■ **A the present invention is applied to the bark as a basal spray, to the vegetation as a foliar spray or to the total surface area of the brush when leaves are not present as a dormant stem spray.

The term "basal application" refers to the application of a herbicide to the base portion of a plant or tree, while the term "basal field spray or concentrate" refers to a composition for basal application.

The term "foliar application" refers to the application of a herbicide to the total foliage of brush and is carried out by aerial or ground spraying. The term "dormant stem application" refers to the application of a herbicide to 'the total surface of 15 brush when the leaves are not present.

The term "brush" refers broadly to any deep rooted perennial broadleaf plant such as trees, bushes and weeds having a woody bark-like stem or trunk covering and is inclusive of seedling trees and other woody 20 vegetation six inches (15.24 cms) in height or greater.

The term "kill and control" means eradication and/or severe stunting of the brush treated according to the invention and sensitive to the herbicide used. The kill and control effect is evidenced by, e.g., 25 brownout and topkill of the treated woody vegetation. Brownout refers to leaves on such vegetation turning from a green color to brown. Topkill refers to the killing of the apical and adjacent top portions of the treated woody vegetation. Kiil and control of brush 30 in an area means eradication and/or severe stunting 29,433-F of substantially all of the undesired brush and other woody vegetation, in the treated area, which is sensitive to the herbicide employed.

It has been unexpectedly found that when one or more glycol ether solvents of the present invention are combined as described herein, with a brush-controlling herbicide and water, that a herbicidal emulsion is formed having substantially the same herbicidal activity as conventional basal or dormant stem sprays while at the same time containing no, or at least significantly lower concentrations of, petroleum distillate type solvents. The glycol ether solvent provides for penetration of the herbicide composition through the bark of the brush or other woody vegetation.

Surfactants are optionally added to the present compositions to aid in penetration of the herbicide. Glycol ether containing foliar sprays also provide control of brush under stress such as draught conditions and late in the growing season.

The glycol ether solvents of Formula I are liquids with the following range of properties: Viscosity (25°C) 1.6 to 25 centistokes Density (25/25°C) Pour point . . . -20°F to 150°F (-29°C to 65.6°C) 0.880 to 1.120 Boiling point . 760 mm Hg 10 mm Hg 115-290°C 20-130°C .

Flash point (°F closed cup) . . . 90-270°F (32-132 °C) 202684 The glycol ethers employed in the practice of the present invention are known compounds and are generally prepared by the reaction of alkylene oxides with alcohols or phenols employing procedures well known in the art.

Some commercially available glycol ethers are the DOWANOL® solvents produced by The Dow Chemical Company such as DOWANOL® TPM, DOWANOL® TEH, DOWANOL® DE, DOWANOL® TBH, DOWANOL®. DB and Dowfroth® 250. A preferred glycol ether is DOWANOL® TPM. A description 10 of these DOWANOL® solvents is contained below: Glycol Ether Solvent Description DOWANOL® TPM DOWANOL® TEH DOWANOL® TBH DOWANOL® DE DOWANOL® DB tripropylene glycol methyl ether triethylene glycol ethyl ether and higher homologs diethylene glycol ethyl ether triethylene glycol butyl ether and higher homologs diethylene glycol butyl ether Dowfroth® 250 polypropylene glycol methyl ether (average molecular weight of about 250) Dowanol® EM Dowanol® DPM Dowanol® PM Dowanol® DM Dowanol® EE Dowanol® EB Dowanol® TMH propylene glycol methyl ether dipropylene glycol methyl ether ethylene glycol methyl ether ethylene glycol ethyl ether ethylene glycol n-butyl ether diethylene glycol methyl ether triethylene glycol methyl ether and higher homologs 202684 Glycol Ether Solvent Description Dowanol® PiB-T propylene glycol isobutyl ether and higher homologs ethylene glycol phenyl ether Dowanol® EPH Dowanol® PPH propylene glycol phenyl ether Other glycol ethers contemplated by the present invention include: the Cellosolve® products available from Union Carbide; the Ektasolve® products 10 available from Eastman; the Poly-Solv® products available from Olin; the Jeffersol® products available from Jefferson and the Oxitol® products available from Shell Oil. in the present composition include the presently known herbicidal phenoxyalkanoic acids, pyridinyloxyalkanoic acids, benzoic acids, picolinic acids or phosphonic acid derivatives or combinations of two or 'more of said herbicides. Examples of such herbicides include 2,4,5-20 trichlorophenoxyacetic acid (2,4,5-T), 2,4-dichloro- phenoxyacetic acid (2,4-D), 2,4-dichlorophenoxypropionic acid (2,4-DP) , 2-msthyl-4-chlorophenoxyacetic acid (MCPA), 2— (4— chloro-o-cresyl) -oxypropionic acid (MCPP) , silvex, triclopyr, dicamba, picloram, 3,6-dichloropicolinic acid and glvphosate. The above-25 mentioned herbicides are usually compounds in the form of esters or salts. Particularly effective herbicides include mixtures of an ester of 4-amino-3,5,6-trichloropicolinic acid and an ester of 2,4,5-T. An especially preferred herbicide is triclopyr which is commercially available 30 as GARLON® 4 herbicide from The Dow Chemical Company.

Suitable brush-controlling herbicides employed The herbicides used in making up the compositions of the invention are conventionally and conveniently supplied in the form of concentrated solutions in inert solvents such as heavy aromatic naphtha having a distil-5 lation range from 160° to 293°C, methanol, toluene or water. As a consequence, the present compositions, as a practical matter, contain such inert solvents although the presence of such solvents is not essential to the performance of the final aqueous spray compositions of 10 the invention.

Acceptable surfactants employed in the present composition include one or more surfactants of one or more of the following classes: (i) a combination of alkaryl polyoxethylene 15 glycol mixed with a petroleum distillate, alkyl sulfate, and alkylamine acetate; (ii) polyalkylene oxide block copolymer; (iii) blend of polyamine salt and a metal salt of alkyl aromatic sulfonic acid with polyoxyalkylene 20 glycol; and (iv) ethoxylated alcohols.

Exemplary of the surfactants of class (i) above is the commercially available product TRONIC® surfactant, hereinafter more fully characterized, which 25 is also a preferred surfactant.

The suitable polyalkylene oxide block copolymers of class (ii) above, such as polyoxyethylene polyoxy-propylene block copolymers, have a molecular weight of from 1000 to 14,000 and preferably have a polyoxyethylene 30 oxide content of from 10 to 80 percent by weight. A preferred surfactant of this class is a polyoxyethylene polyoxypropylene block copolymer of the formula: 29,433-P ^ ^ s? ® /I ■ <. ^ -r, g 4 HO (CHoCHo0 ) a (CHCHo0). (CH„CHo0 ) H 2 2a, 2 d 2 2 c CH3 wherein b is a whole number greater than 14 and a and c 5 are whole numbers selected so that the polyoxyethylene portion amounts to from 20 to 80 percent by weight of the polymer. An especially preferred compound is a polyoxyethylene polyoxypropylene block copolymer having about 40 percent by weight polyoxyethylene content and 10 a molecular weight of about 4,400 which is available commercially as PLURONIC® L-64 surfactant from BASF Wyandotte Inc.

Suitable blends of polyamine salts and metal salts of alkylaromaticsulfonic acid with polyoxyalkylene 15 glycol of class (iii) above are described in Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Vol. 19:503-593 and are also described in U.S. Patent 2,898,267.

Examples of the alkylaromaticsulfonic acid portion of the surfactant blends are the polyamine 20 salts and metal salts of dodecylbenzenesulfonic acid or tridecylbenzenesulfonic acid wherein the polyamine has from two to four carbon atoms between amine groups and the metal ion is an alkali metal or alkaline earth metal cation.

Examples of the polyalkylene glycol portion of the surfactants are polyglycol ethers of nonylphenol having from 8 to 40 oxyethylene groups and polyoxyethylene ethers of dodecylphenol having from 8 to 40 oxyethylene groups. A preferred surfactant is 30 SPONTO® 712, a commercially available product, which ? ^ ^ ^ ffl a - •• o o 4 comprises about 25 mole percent nonyl phenol having about 15 ethylene oxide groups per polymer molecule in combination with polyamine salts and metal salts of dodecylbenzenesulfonic acid.

An example of an ethoxylated alcohol is tridecyl alcohol plus 8-9 moles of ethylene oxide per mole of tridecyl alcohol.

Examples of surfactants of each of the classes herein specified and employed in the present invention 10 are described in Kirk-Othmer, supra.

Other acceptable surfactants are the commercially available agricultural spray adjuvants which contain surfactants such as SURFEL® or other crop oil concentrates.

At least one of each of the herbicides, glycol ether solvents and optionally a surfactant, all described herein, are admixed to form a herbicidal concentrate useful in making herbicidal spray compositions. This herbicidal concentrate is mixed with 20 water to form an emulsion. A preferred glycol ether solvent is tripropylene glycol methyl ether. While the order in which these ingredients are to be mixed is not critical, it is advantageous to first mix the herbicide, glycol ether and optionally a surfactant to form the 25 concentrate and then dilute it with water. When diluting the concentrate it is advantageous to slowly add it to about half the total amount of water that will be present in the spray with continuous agitation after which the other half of the water is then added. This 30 method of preparing the spray facilitates the formation , 133 -F -8- --9- 202684 of smooth emulsion. If the water is added to the herbicide/glycol ether/surfactant concentrate, a thick invert or water-in-oil emulsion may form which may be hard to convert to a normal emulsion. The field spray 5 thus prepared is then applied using known basal application technigues for the kill and control of brush. Alternatively, the spray compositions of the present invention may be applied as a foliar spray or as a dormant stem spray for the kill and control of brush.

The above-mentioned spray compositions contain the following varying percentages by volume of ingredients: a formulated herbicide (including . . . 0.01-50% solvents and inerts) glycol ether solvent ......... 0.1-60% water ........ 20-98% surfactant 0-20% petroleum distillate solvent (oil) . . 0-25% In a basal spray operation a preferred amount of glycol ether solvent present in the spray composition is from 20 20 to 50 percent by volume and in a foliar spray operation a preferred amount of glycol ether solvent present in the spray composition is from 5 to 15 \ percent by volume. In a dormant stem spray composition a preferred amount of glycol ether solvent 25 present in the spray composition is from 1 to 5 percent by volume. The amounts of ingredients selected for brush-controlling operations will vary and depend on a variety of factors such as, for example, the individual herbicide, glycol ether and surfactant 30 employed and the optimum concentration is determined by techniques known in the art, i.e., dose^^lpE^t^on C // r 2026?4 determinations. When the herbicide is triclopyr and the glycol ether is tripropylene glycol methyl ether, a preferred basal spray composition contains the tripropylene glycol methyl ether in an amount in the range of from 20 to 60 percent by volume and further contains up to 20% by volume of an acceptable surfactant, and a preferred foliar or dormant stem spray composition contains the tripropylene glycol methyl ether in an amount in the range of from 0.5 to 10% by volume.

A specific example of a suitable herbicidal basal spray mixture, by volume, contains (a) 2% GARLON0 4 brand triclopyr herbicide containing 4 pounds triclopyr per gallon f. 48 kg/L), (b) 25% DOWANOL® TPM brand tripropylene glycol methyl ether, (c) 1.0% SPONTO® 712 brand surfactant and 72% water.

This preferred herbicidal spray emulsion is effective for the kill and control of brush at an application rate of about 100 gallons/acre (935.4 L/ha).

The present invention provides an aqueous basal spray having an efficacy of penetration of the brush killing herbicide component thereof through bark substantially equal to that of conventional petroleum distillate type oil-basal sprays while using no, or substantially less, petroleum distillates. Effective basal sprays using no or small amounts of petroleum distillates are made by using as a spray adjuvant one or more of the herein-defined glycol ethers. The basal sprays described herein provide penetration of the herbicide component through the bark of a tree when said basal spray is contacted with the bark of the tree. To eradicate or greatly suppress the growth of the undesired woody vegetation a sufficient amount of spray is preferably employed to wet the bark around the base of the plant. Ordinarily, from 1 to 400 gallons of spray is employed to treat 1 acre of brush or other woody vegetation, (9.3 54 to 3741.6 L/ha) the exact amount depending on such factors as the density, type and size of the brush. Generally, about 100 gallons is employed / per acre treated (935.4 L/ha). The amount of spray that is more cost effective varies depending on the C. herbicide and amount of herbicide present in the spray. 2026 It is not critical that the basal herbicidal sprays of the present invention be applied to the brush at a specific growing stage that the brush is in, i.e., budding stage, dormancy stage, flowering stage, etc.

Application during any stage will be effective. For ease of application, it is preferred to apply the present basal sprays while the brush is in the dormant stage in moderate climates where snow will not effect basal application. In the more severe winter climate 10 areas where the presence of snow will prevent the basal application of herbicides when plants are in a dormant stage then application of the present herbicidal con-position is preferably carried out in the months in which snow is not likely.

The following examples illustrate the present invention and the manner by which it can be practiced.

Example 1 Herbicidal compositions according to the present invention were tested for herbicidal activity 20 by applying them to 54 day old cotton plants hardened in a greenhouse. The cotton plants were from 15 to 20 inches (38.1 to 50.8 cms) in height. Three (3) plant per treatment were used and, after application of the herbicidal composition, were stored in a greenhouse. 25 The herbicidal compositions were rated 3 days and 6 weeks after application. Ratings were based on visual observation of the 3 plants based on percent brownout which refers to the percent dead or burned portion of the leaves and stem. The 6 week rating 30 in addition to a brownout rating also included a rating on new growth which refers to any visual signs of new leaves or buds.

The herbicidal compositions were prepared by the following order of addition of components: (1) GARLON® 4 brand triclopyr herbicide, (2) surfactant, (3) glycol ether, and (4) a portion of the required water.

The above components were agitated until thoroughly mixed before the addition of the next component. Enough water was added to complete the final spray volume of 100 gallons 10 (378.5 L).

The GARLON® 4 brand triclorpyr herbicide is a commercially available product and contains 4 pounds (lb) triclopyr acid equivalent per U.S. gallon (0.48 kg/L).

The surfactants employed in the herbicidal 15 compositions were SPONTO® 712 (Witco Chemical Co.), TRONIC® (Colloidal Products) or ETHOSPERSE® TDA-6, all commercially available products.

The glycol ethers employed in the herbicidal compositions were the following commercially available 20 products: Glycol Ether DOWANOL® TPM DOWANOL® TEH DOWANOL® DE DOWANOL® TBH DOWANOL® DB DOWFROTH® 250 Description tripropylene glycol methyl ether triethylene glycol ethyl ether and highers diethylene glycol ethyl ether triethylene glycol butyl ether and highers diethylene glycol butyl ether polypropylene glycol methyl ether A0' - /"> ■: / ^ rn /j The herbicidal compositions were made up in 100 gallon (378.5 L) batches and applied to the cotton plants using a Greenhouse Track Sprayer with a 8010 tee jet nozzle at 40 lbs. psi (275.8 kilopascal) and 3 mph 5 (4.827 km/hr). 67 Treatments were tested wherein the controls consisted of (a) herbicide mixed in water alone, (b) herbicide mixed in No. 1 diesel oil alone and (c) herbicide, No. 1 diesel oil and SPONTO® 712 mixed 10 together. Results are listed in Table I. ,133 -P GARLON® 4 Treatment Number Glycol Ether** (liters) Brand triclop; (liters TPM 1 37 .85 0. .473 2 37 .85 0. .473 3 37 .85 0, .473 4 37 .85 0. .946 37 .85 0. .946 6 37 .85 0, .946 7 56 .78 0, .473 8 56 .78 0, .473 9 56 .78 0, .473 TEH 37 .85 0. .473 11 37 .85 0, .473 12 37 .85 0, .473 13 37 .85 0. .946 14 37 .85 0. .946 37 .85 . 0. .946 16 56 .78 0, .473 17 56 .78 0, .473 18 56 .78 0. .473 TABLE 1 Surfactant* (3.7854 liter each) S T E S T E S T E S T E S T E S T E 3 Day Results Percent Brownout 6 Week Results Percent New Brownout Growth 70 None 60 None 40 60 None 80 None 40 90 None 60 90 None 60 None 40 60 None 40 70 None 60 None 60 None 40 70 None 100 None 40 70 None None 80 None 40 80 None 60 80 Yes GARLON® 4 Glycol Brand Treatment Ether** triclopyr Number (liters) (liters) DE 19 37.85 0.473 37.85 0.473 21 37.85 0.473 22 37.85 0.946 23 37.85 0.946 24 37.85 0.946 56.78 0.473 26 56.78 0.473 27 56.78 0.473 TBH 28 37.85 0.473 29 37.85 0.473 37.85 0.473 31 37.85 0.946 32 37.85 0.946" 33 37.85 0.946 34 56.78 0.473 56.78 0.473 36 56.78 0.473 TABLE 1 Con'd 3 Day Surfactant* Results (3.7854 Percent liter each) Brownout 6 Week Results Percent Brownout New Growth S 0 50 None T 20 70 None E 40 80 None S 20 80 None T 20 90 None E 40 90 None S 20 80 None T 40 60 None E 40 80 None S 80 70 None T 80 70 None E 80 60 None S ' 80 70 None T 80 90 None E 80 90 None S 80 40 None T 80 80 Yes • E 80 60 None TABLE 1 Con1d GARLON® 4 3 Day Treatment Number Glycol Ether** (liters) Brand triclopyr (liters) Surfactant* (3.7854 liter each) Results Percent Brownout 6 Week Results Percent New Brownout Growth DB 37 37. 85 0. .473 S 40 70 None 38 37. 85 0. .473 T 60 70 None 39 37. 85 0, .473 E 60 80 None 40 37. 85 0. .946 S 40 90 None 41 37. 85 0. .946 T 40 90 None 42 37. 85 0, .946 E 80 100 None 43 56. 78 0, .473 S 60 80 None 44 56. 78 0. .473 T 60 70 Yes 45 56. 78 0. .473 E 80 70 None PPM- •250 46 37. 85 0, .473 S 80 80 None 47 37. 85 0, .473 T 80 90' None 48 37. 85 0. .473 E 80 90 None 49 37. 85 0. .946 S 80 100 None 50 37. 85 0. .946 T 80 90 None 51 37. 85 0. .946 E 80 90 None 52 56. 78 0, .473 S 80 70 None 53 56. 78 0. .473 T . 80 80 Yes 54 56. 78 0. .473 E 80 80 None Treatment Number Control 55 56 57 58 Glycol Ether** (liters) None None Oil-99.875 Oil-56.78 GARLON® 4 Brand triclopyr (liters) 0.473 0.946 0.473 0.473 62 TPM (37 .85) 0. 946 63 TEH (37 .85) 0. 946 64 DE (37 .85) 0. 946 65 TBH (37 .85) 0. 946 66 DB (37 .85) 0. 946 67 PPM- ■250 (37 .85) 0. 946 *Surfactant identification: TABLE 1 Con'd Surfactant* (3.7854 liter each) 3 Day Results Percent Brownout 6 Week Results Percent Brownout New Growth None None None S 0 0 80 0 70 70 100 70 None None None None None None None None None 40 20 60 60 90 90 70 70 80 None None None None None None 60 90 None s= T= E= SPONTO® 712 TRONIC® ETHOSPERSE® TDA-6 **Glycol ether identification TABLE 1 Con1d TPM = tripropylene glycol methyl ether TEH = triethylene glycol ethyl ether and highers DE = diethylene glycol ethyl ether TBH = triethylene glycol n-butyl ether and highers DB = diethylene glycol n-butyl ether PPM-250 = polypropylene glycol methyl ether with average molecular weight of 250. 4 Example 2 - Control Field Spray The following herbicidal field spray is prepared as a control: Butoxyethyl ester of triclopyr .... 7.57 liters 5 (4 lbs/gallon (0.48 kg/L) and containing 38.4% petroleum distillate and inerts) Oil (diesel or fuel) 370.97 liters 378.54 liters Example 3 - Basal Field Spray Free of Petroleum Distillates The following basal field spray emulsion is prepared employing substantially the same procedure 15 of Example 1 by mixing the following ingredients: Butoxyethyl ester of triclopyr . . (4 lbs/gallon (0.48 kg/L) and containing 38.4% petroleum distillates and inerts) 7.57 liters Tripropylene glycol methyl ether. . . 94.64 liters SPONTO® 712 3.78 liters Water 272.55 liters 378.54 liters 29,433-F Example 4 - Basal Field Spray The following ingredients are used to prepare a basal field spray: Butoxyethyl ester of triclopyr .... 3.785 liters 5 (4 lbs/gallon (0.48 kg/L) and containing 38.4% petroleun distillates and inerts) Polypropylene glycol methyl ether (avg. molecular weight of 250). . 94.64 liters SPONTO® 712 3.785 liters The above field spray is prepared by mixing the triclopyr 15 and polypropylene glycol methyl ether with constant agitation. The SPONTO® 712 is then added, also with constant agitation, to form a concentrate. A spray tank equipped with an agitator is filled to the 50 gallon (189.27 liters) mark with water and then the 20 concentrate is slowly added to the water with continuous agitation. After the addition of the concentrate, the balance of the water is added to form 100 gallons (378.54 liters) of field spray.

Example 5 The field spray of Example 4 is applied to one acre (0.4 hectare) of brush using a knapsack sprayer using a pressure of 30 pounds per square inch (206.84 kilopascals). The basal parts of brush and tree trunks Water 276.33 liters 378.54 liters ■2:0,433-F ^ ; - '. . j are sprayed to a height of 12 to 15 inches (30 to 38 cms) from the ground. More spray is applied to old or rough bark than is applied to smooth young bark. Substantially the same effective kill and control of the brush is 5 accomplished as that of the control field spray of Example 2 when applied in a similar manner.

Example 6 basal field spray of Example 3 are applied to brush in 10 substantial accordance with the procedures of Example 5. Both the control and basal field spray produce comparable kill and control of brush.

Example 7 - Foliar or Dormant Stem Spray Composition The following ingredients are used to prepare 15 a herbicidal spray composition useful for either ground foliar application to brush or dormant stem application to brush.

The control field spray of Example 2 and the Butoxyethyl ester of triclopyr 2.839 liters Tripropylene glycol methyl ether . . . 3.7854 liters Water 371.9168 liters 378.5412 liters The above spray is applied to brush at a rate of about 100 gallons/acre (935.4 L/ha) but this amount may vary ,133 F- depending on the density, type and size of the brush to be treated. This spray is particularly suitable for spraying right-of-ways adjacent to utility lines, highways and railroads. 202684

Claims (3)

1. WHAT WE CLAIM IS: 1. A herbicidal spray composition comprising: (a) an effective amount of at least one brush controlling herbicide; (b) from 0.1 to 60 percent by volume of at least one glycol ether of the formula R-O-(CHoCH0) H x 2 'n wherein R represents C^_C4 alkyl or phenyl, each R^ independently represents hydrogen, methyl or ethyl, and n represents any one of the integers 1 to 10, inclusive; and (c) from 20 to 98 percent by volume water.
2. 2. The herbicidal spray composition of Claim 1 wherein the herbicide is an ester or salt of triclopyr, 2,4,5-T, 2,4-D, picloram, 2,4-DP,MCPA, MCPP, 3,6-dichloropicolinic acid, glyphosate or combinations thereof. -23- + / ■;/'V -24- 202684 3. The herbicidal spray composition of claim 1 or Claim 2 wherein the glycol ether solvent is tripropylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol butyl ether, diethylene glycol butyl ether or combinations thereof. 4. The herbicidal spray composition of any one of Claims 1 to 3 further comprising up to 20 percent by volume of one or more acceptable surfactants. Claim 4 wherein the surfactant is a polyoxyethylene polyoxypropylene block copolymer having a molecular weight of about 4,400 and a polyoxyethylene content of about 40 percent by weight. Claim 4 wherein said surfactant is a blend of a polyamine salt and metal salt of dodecylbenzenesulfonic acid with nonylphenyl polyoxyethylene having about 15 oxyethylene groups per polymer molecule. Claim 4 wherein said surfactant is tridecyl alcohol plus 8-9 moles of ethylene oxide per mole of tridecyl alcohol.
3. 3. The herbicidal spray composition of any one of Claims 1 to 7 wherein said herbicide is present in an amount of from 0.01 to 50 percent by volume. 5. The herbicidal spray composition of 6. The herbicidal spray composition of 7. The herbicidal spray composition of 9. The herbicidal spray composition of triclopyr, Claim 1 which is a basal spray composition wherein t/ ^ (a) said brush controlling herbicide is,^ triclopvr, ^ -24- -25- 202684 (b) said glycol ether is tripropylene glycol ; methyl ether present in an amount in the range of from : 2 0 to 60 percent by volume and further comprising up to 20 percent by volume of an acceptable surfactant. 10. The herbicidal spray composition of Claim 1 which is a foliar or dormant stem spray composition wherein (a) said brush controlling herbicide is triclopyr, (b) said glycol ether is tripropylene glycol methyl ether present in an amount in the range of from 0.5 to 10 percent by volume. 11. A method for the kill and control of brush which comprises contacting the brush to be controlled with an amount of a canposition of any one of Claims 1 to 10 effective to kill and control said brush. 12. The method of Claim 11 wherein said contacting is accomplished by basal.application of said herbicidal spray composition. 13. The method of Claim 12 wherein said basal application is carried out when said brush is in a dormant stage. 14. The method of Claim 11 wherein said contacting is accomplished by foliar application of said herbicidal spray composition. 15. The method of Claim 11 wherein said contacting is accomplished by dormant stem application of said herbicidal spray composition. DATEu TM!S /?/£■ DAY OFvSWg-S~ A . J . P " r. i< ?•. RONv 25 i- / i J/ - ■£ - A;'.: •: : "c.. . .. v'"'-'cants