a2) United States Patent
`US 6,875,381 B2
`(10) Patent No.:
`Apr. 5, 2005
`(45) Date of Patent:
`Jadhavet al.
`
`US006875381B2
`
`(54)
`
`PROCESS FOR PREPARATION OF
`CHEMICALLY STABLE, DRY-FLOW, LOW
`COMPACT, DUST FREE, SOLUBLE
`
`(75)
`
`PHOSPHOROAMIDOTHIOATES
`.
`Inventors: PrakashMahadeo Jadhav, Mumbai
`(IN); Rajju Devidas Shroff, Mumbai
`(IN)
`
`(73)
`
`Assignee: United Phosphorus, Ltd., Mumbai
`(IN)
`
`(*)
`
`Notice:
`
`5,352,674 A
`10/1994. Cummings
`5,369,100 A
`11/1994 Cummings
`5,443,764 A
`8/1995 Lloyd
`;488,043 A
`1/1996 Yamada
`5,622,658 A
`4/1997 Lloyd
`5,650,163 A
`7/1997 Cannel
`5.698.540 A
`12/1997 Katayama
`6,013,272 A
`‘1/2000 Cummings
`6,337,323 B2
`1/2002 Cummings
`6,387,388 B1
`5/2002 Misselbrook
`2001/0018063 Al
`8/2001 Cummings
`2002/0091106 A1
`7/2002 Cummings
`2002/0114821 At
`8/2002 Lescota
`FOREIGN PATENT DOCUMENTS
`
`Subject to any disclaimer, the term ofthis
`patent is extended or adjusted under 35
`
`US.C. 154(b) by 367 days. 0304492 Bl=12/1994EP
`
`JP
`58067603
`4/1983
`JP
`6-92803
`4/1994
`IP
`9.104406
`5/1997
`WO
`WO 98/26656
`6/1998
`OTHER PUBLICATIONS
`
`.
`Appl. No.: 10/126,965
`Filed:
`Apr. 22, 2002
`Prior Publication Data
`
`(21)
`
`(22)
`
`(65)
`
`(60)
`
`(51)
`(52)
`(58)
`
`(56)
`
`US 2003/0127761 A1 Jul. 10, 2003
`
`Related U.S. Application Data
`Provisional application No. 60/340,272, filed on Dec. 18,
`2001.
`
`Tint. C17 oicccccccccccceececseseeneecsssnseeens B29B 9/00
`U.S. Che cieecccccecceeseeseeteeeneeeeeee 264/37.29; 264/140
`Field of Search ...............ccceceeees 514/120, 137,
`514/75; 424/710; 264/37.29, 140, 330
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`3,716,600 A
`3,845,172 A
`3,914,417 A
`4,218,444 A
`4,544,553 A
`5,075,058 A
`5,100,667 A
`5,298,501 A
`
`2/1973 Magee
`10/1974 Magee
`10/1975 Magee
`8/1980 Koundakjian
`10/1985 Smolanoff
`12/1991 Chan
`3/1992 Chan
`3/1994 Cummings
`
`International Specialty Products, “Granules & Tablets,”
`Agrimer Polymers & Copolymers, International Specialty
`Products.
`
`Fuji Paudal Co., Ltd., “Powder & Granulation Process
`Technology,” Fuji Paudal Co., Ltd.
`
`Primary Examiner—Mark Eashoo
`(74) Attorney, Agent, or Firm—Jones, Tullar & Cooper, PC
`
`(57)
`
`ABSTRACT
`
`low compact, dust free, soluble granules of
`Dry flow,
`phosphoroamidothioates, preferably acephate, are produced
`by the process of 1) pre-mixing technical grade phospho-
`roamidothioate with specified adjuvants and other inert
`ingredients; 2) grinding to produce a ground product having
`a preferred particle size of 5 microns to 10 microns; 3)
`post-mixing; 4) granulating; 5) drying; 6) sizing to required
`length, preferably 1.5 to 3.0 mm; 7) and sieving to remove
`the fines to get the desired dust free soluble granule.
`
`68 Claims, 1 Drawing Sheet
`
`8
`Ls
`-
`
`
`Wetting
`Dispensing
`gest
`Agent
`Tasectcidaly
`
`
`
`
`
`
`
`
`
`
`
`
`74
`Xt
`PREMIXING
`
`
`
`
`
`_As
`
`
`GRINDING
`|_A4 ¥
`POSTMIXING
`
`CHARGING
`
`GRANULATION
`|_Ab ¥
`
`SIZING
`|At
`y
`DUSTFREE
`FINES
`
`SIEVING
`SOLUBLE
`
`GRANULES
`
`
`
`L
`
`
`
`
`DRYING ¥
`
`
`TIDE 1018
`
`1
`
`TIDE 1018
`
`

`

`U.S. Patent
`
`Apr. 5, 2005
`
`US 6,875,381 B2
`
`2
`
`4
`
`6
`
`8
`
`Dispersing
`
`Wetting
`
`Binding
`
`10
`——
`
`Active
`compound
`
`Disintegrating
`
`'
`
`4
`
`PREMIXINGnese 8
`
`0
`
`GRINDING
`
`4
`
`2
`
`6
`
`POST MIXING
`
`28
`
`GRANULES
`
`DUST FREE
`SOLUBLE
`
`2
`
`

`

`US 6,875,381 B2
`
`1
`PROCESS FOR PREPARATION OF
`CHEMICALLY STABLE, DRY-FLOW, LOW
`COMPACT, DUST FREE, SOLUBLE
`GRANULES OF
`PHOSPHOROAMIDOTHIOATES
`
`CROSS REFERENCE TO RELATED
`APPLICATION
`
`This application claims the benefit, under 35 U.S.C.
`119(e), of U.S. Provisional Application No. 60/340,272filed
`Dec. 18, 2001, the contents of which are incorporated herein
`by reference.
`BACKGROUNDOF THE INVENTION
`
`1. Field of the Invention
`
`The present invention relates to a process for preparing
`insecticidally active soluble granules of
`phosphoroamidothioate, referred to herein as acephate.
`2. Background Information
`In recent years, agricultural chemicals have been most
`preferably formulated in the form of dusts, wettable
`powders, soluble powders, emulsifiable concentrates,
`soluble liquid/concentrates, granules, coated granules, water
`dispersible granules, suspension concentrates, and solutions.
`Occasionally, when dusts are produced by absorbing or
`mixing active ingredients with a finely divided inert carrier
`material, for example China Clay or the like, drift problems
`occur. With wettable powders and soluble powders the
`problemsfaced at the time of dilution are not only drift, but
`the final disposal of containers, for dust particles tend to
`stick to sides of the containers. The left over materials within
`the containers pose great problems to the environment,
`operators and users.
`Although dusts are undesirable because of airborne con-
`tamination and handling difficulties, liquid spray formula-
`tions have not provided an acceptable alternative, for they
`involve solvents and packaging expenses, along with con-
`tainer disposal requirements that detract from their commer-
`cial desirability.
`Water dispersible granules produced by fluidized bed
`spray dryers overcome the problems associated with wet-
`table powders and soluble powders, but have high process-
`ing costs and require high value capital investment, as well
`as requiring highly skilled staff. These problems impose a
`significant barrier in widening the market acceptance of
`these compounds.
`and
`Certain
`phosphoroamidothioates
`phosphoroamidodithioates, collectively referred to as
`Phosphoroamidothioates, are knownto have excellent insec-
`ticidal activity against a variety of insects and in a variety of
`environments. Acephate, one of the important commercial
`insecticides within this class of compounds, is a systemic
`and contact insecticide of moderate persistence with residual
`activity lasting about 10-15 days.It is effective against a
`wide range of aphids,
`leaf-miners,
`lepidopterous,
`larvae,
`sawflies and thrips andit is also a non-phytotoxic on many
`crop plants.
`Phosphoroamidothioate containing pellets have been pro-
`posed in the past, but difficulties have been encountered in
`pelletizing acephate technical,
`the preferred insecticide
`within the class of phosphoroamidothioates. Attempts to
`manufacture acephate technical pellets from acephate tech-
`nical powders have been proposed and have been unsuc-
`cessful.
`
`Considerable experimentation in the area of producing the
`preferred high-strength acephate granules has been con-
`ducted and confirms the manufacturing difficulties which
`earlier formulators have experienced. Furthermore, the pel-
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`55
`
`60
`
`65
`
`2
`lets and methods proposed for making pellets suggested in
`the prior art leave considerable room for improvement. Prior
`extrusion processes have proposed the addition of costly
`surfactants, the combination of phosphoroamidothioate with
`a second active ingredient, or the creation of a mixture of the
`active ingredient with a solvent in an amountof from 3-25%
`by weight before extrusion, but these processes have not
`solved the problems encountered.
`The formulation of acephate presently in use is acephate
`75% soluble powder having acephate active ingredient 75%
`(w/w), surfactant 1 to 2% (w/w), inert filler (precipitated
`silica) to make 100% (w/w). Acephate 75% soluble powder
`poses the problems of dust, low pourability, high transpor-
`tation costs, high capital manufacturing investment, mea-
`surement difficulties, difficulties in packing material
`disposal, handling problems,high risk of caking and others.
`Because of the problems associated with producing
`granular forms of phosphoroamidothioates, such as the
`preferred acephate, there is a need in the art for a process for
`preparing chemically stable, dry flow, low compact, dust
`free, insecticidally active soluble granules of phosphoroa-
`midothioate which are useful from a practical stand point, as
`well as for a low cost, practical manufacturing technique
`which can be practiced on a commercial scale without
`requiring expensive additives or solvents.
`SUMMARYOF THE INVENTION.
`
`Bythe present invention the above-identified major limi-
`tations have been overcome. The method for producing dry
`flow, low-compact, dust free, soluble phosphoroamidothio-
`ate granules, such as the preferred compound acephate,is an
`improvement over prior manufacturing processes. Further,
`the dust free soluble granules produced by this invention,
`which has a concentration of the insecticidally active ingre-
`dient in this formulation may vary from 40-98% of phos-
`phoroamidothioate active ingredient, is more advantageous
`than prior granular products and exhibits certain very desir-
`able characteristics as noted hereinafter.
`
`Briefly, and in accordance with a preferred embodimentof
`the invention, dry flow,
`low compact, dust free, soluble
`granules of insecticially active phosphoroamidothioate are
`prepared by forming a pre-mix containing the required
`quantity of phosphoroamidothioate, a dispersing agent, a
`wetting agent, a binding agent, an antifoaming agent, a
`disintegrating agent, a stabilizer and filler. The specified
`adjuvants have a maximum of 1% water insoluble matter.
`This pre-mix is then ground to produce a ground product
`having preferred particle sizes between 5.0 microns to 10.0
`microns. The ground productis fed to a post-mixer to form
`a mixture. The mixture is then fed through a hopperinto a
`granulator where granules are formed. The granules are then
`dried, and the dried granules are sized and sieved to separate
`dry granules from fines, producing dry flow, low compact,
`dust free, soluble granules of phosphoro-amidothioate as
`noted above, the preferred phosphoroamidothioate is aceph-
`ate. The fines may be recycled back to the post mixer.
`low
`This invention produces essentially dry flow,
`compact, dust free soluble phosphoroamidothioate granules
`having a preferred granule size of 1.5 to 3.0 mm in length
`and 0.5 to 1.0 mm in diameter. These granules of phospho-
`roamidothioates are characterized by aging stability for a
`minimum of two years.
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`The features and advantagesof the present invention will
`becomeapparent from the following detailed description of
`preferred embodiments thereof, taken in conjunction with
`the accompanying drawings, in which:
`FIG. 1 is a flow chart of the preferred embodimentof the
`present invention.
`
`3
`
`

`

`US 6,875,381 B2
`
`3
`DETAILED DESCRIPTION OF THE
`PREFERRED EMBODIMENTS
`
`The process of the present invention is best described by
`referring to the flow chart m FIG. 1. An essentially dry
`pre-mix comprising about 95% to 99% of solids and 1% to
`5% moisture and/or solvent is formed from the following
`ingredients: 40% to 98% of the insecticidally active com-
`pound 2, 0.1% to 5.0% dispersing agent 4, 0.1% to 3.0%
`wetting agent 6, 0.1% to 3.0% binding agent 8, 0.01% to
`0.08% antifoaming agent 10, 0.01% to 10.0% disintegrating
`agent 12, 0.01% to 1.0% stabilizer 14,andfillers 16 to make
`100% (w/w). The insecticidally active compounds of the
`present invention have the following formula:
`
`R—y °
`\t
`/\Ris
`
`R?
`
`wherein R and R? individually are an alkyl, alkenyl or
`alkynyl group containing upto 6 carbon atoms, R? is
`hydrogen, an alkyl group containing 1 to 18 carbon atoms,
`a cycloalkyl group containing 3 to 8 carbon atoms, an
`alkenyl group containins 2 to 18 carbon atomsor an alkynyl
`group containing 3 to 18 carbon atoms, R? is hydrogen or an
`alkyl group containing 1 to 6 carbon atoms, and Y is oxygen
`or sulfur. All of the inert ingredients are preferably solids
`and in a powder form. In one preferred embodiment, the
`binding agent 8 is selected from sucrose and starch deriva-
`tives or a blend thereof, the wetting agent 6 is selected from
`calcium or sodium salt of alkyl aryl sulphonate, the dispers-
`ing agent 4 is selected from the derivative of sulfonated fatty
`alcohols, the disintegrating agent 12 is selected from swell-
`ing type clays such as Bentonite and zeolite, the antifoaming
`agent 10 is selected from silicon oil derivatives, the stabiliser
`14 is selected from salts of higher fatty acids, and the filler
`16 is selected from precipitated silica and kaoline and the
`like. Grinding 22 of the pre-mix 20 is then conducted,
`preferably in a microniser, to obtain a ground product 24
`having a preferred particle size of 5 microns to 10 microns.
`The ground product 24 is subjected to post-mixing 26 to
`form a mixture 28 which is then made into granules 36 by
`preferably charging 30, by wayofa rotary feeder, a feeding
`hopper which supplies the mixture to a granulator for
`granulation 34. The granulator that performs the granulation
`34 has a preferred inlet temperature between 30 to 35° C.
`and a preferred outlet temperature of between 40° C. to 45°
`C. The resulting granules 36 are subjected to a drying 38
`process, preferably by passing the granules 36 through an air
`chamber, producing dry granules 40.
`Sizing 42 the dry granules 40 is then accomplished to
`produce sized granules 44 of a desired length and diameter.
`Sizing the granules is preferably conducted by passing the
`dry granules 40 through an oscillating cutter to obtain
`granules which are preferably between about 1.5 mm and
`3.0 mmin length and 0.5 mmto 1.0 mmin diameter. After
`sizing, the sized granules 44 are subjected to sieving 46 to
`separate fines 50 generated during the sizing process from
`desired dust free soluble granules 51.
`The fines 50 from the sieving 46 process maybe collected
`and recycled at the charging 30 stage of the process to obtain
`a minimum yield of 99.0% dry flowable, low compact, dust
`free, soluble granules 54 of phosphoroamidothioates, pretf-
`erably acephate.
`The dust free soluble granules 54 were tested for required
`quality specifications and packed in desired packing. This
`technique gives 99% of conversion yield. The dust free
`
`4
`soluble granules 54 enjoy all the formulation advantages
`described above, producing dust free soluble granules 54
`which are beneficial from an economic aspect and a han-
`dling aspect and which show a very good performance
`during use.
`
`The following examplesare presented to illustrate but not
`to restrict the present invention. Parts and percentage are by
`weight unless otherwise specified.
`
`EXAMPLE1
`
`Acephate 97% Granules can be prepared as follows:
`
`Composition
`
`Ingredients
`
`Quantity (% w/w)
`
`Acephate Technical 98.5% purity
`Dispersing agent
`Wetting agent
`Binding agent
`Antifoaming agent
`Disintegrating agent
`Stabilizer
`Filler
`
`Total
`
`98.48
`0.50
`0.10
`0.10
`0.03
`0.50
`0.05
`0.24
`
`100.00
`
`EXAMPLE 1 PROCESS
`
`The constituents of the above composition are mixed in a
`pre-mixer, then ground in a microniser to the required size
`of 5 micron to 10 micron. The ground product 24 is again
`mixed in a post-mixer to get a uniform homogeneous
`mixture 28. This homogeneous mixture 28 is then fed
`through a rotary feeder into a low compaction granulator,
`while maintaining an inlet temperature of 32 to 35° C. and
`an outlet temperature of 40 to 45° C. The Acephate granules
`36 formed in the granulator are further dried through an air
`chamber, sized to 1.5 mm to 3 mm length,andare collected.
`The fines 50 generated during the process are recharged to
`get a conversion yield of 99 percent.
`
`EXAMPLE 2
`
`Acephate 98% granules can be prepared as follows:
`
`Composition
`
`Ingredient
`
`Quantity (% w/w)
`
`Acephate Technical 98.5% purity
`Dispersing agent
`Wetting agent
`Binding agent
`Antifoaming agent
`Disintegrating agent
`Stabilizer
`Filler
`
`Total
`
`99.50
`0.25
`0.03
`0.05
`0.02
`0.05
`0.05
`0.05
`
`100.00
`
`Acephate 98% granules with above composition can be
`prepared by following the process described in EXAMPLE
`1.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`60
`
`a5
`
`4
`
`

`

`6
`EXAMPLE6
`
`US 6,875,381 B2
`
`->
`
`EXAMPLE3
`
`Acephate 97.5% granules can be prepared as follows:
`
`Acephate 75% Granules can be prepared as follows:
`Composition
`
`Composition
`
`Ingredient
`
`Acephate Technical 98.5% purity
`Dispersing agent
`Wetting agent
`Binding agent
`Antifoaming agent
`Disintegrating agent
`Stabilizer
`Filler
`
`Total
`
`Quantity (% w/w)
`98.99
`0.40
`0.10
`0.10
`0.03
`0.20
`0.05
`0.13
`
`100.00
`
`Acephate 97.5% granules with above composition can be
`prepared by following the process described in EXAMPLE
`1.
`
`EXAMPLE 4
`
`Acephate 90% Granules can be prepared as follows:
`
`Composition
`
`Ingredient
`
`Acephate Technical 98.5% purity
`Dispersing agent
`Wetting agent
`Binding agent
`Antifoaming agent
`Disintegrating agent
`Stabilizer
`Filler
`
`Total
`
`Quantity (% w/w)
`91.38
`00.75
`00.10
`00.20
`00.03
`01.00
`00.50
`06.04
`
`100.00
`
`Acephate 90% granules with above composition can be
`prepared by following the process described in EXAMPLE
`1.
`
`EXAMPLE5
`
`Acephate 85% granules can be prepared as follows:
`
`Composition
`
`Ingredient
`
`Acephate Technical 98.5% purity
`Dispersing agent
`Wetting agent
`Binding agent
`Antifoamer
`Disintegrating agent
`Stabilizer
`Filler
`
`Total
`
`Quantity (% w/w)
`86.30
`01.50
`00.50
`01.00
`00.05
`02.00
`00.60
`08.05
`
`100.00
`
`5
`
`10
`
`15
`
`25
`
`30
`
`35
`
`Ingredient
`
`Quantity (% w/w)
`
`Acephate Technical 98.5% purity
`Dispersing agent
`Wetting agent
`Binding agent
`Antifoaming agent
`Disintegrating agent
`Stabilizer
`Filler
`
`Total
`
`76.15
`2.00
`1.50
`1.50
`0.06
`5.00
`0.75
`13.04
`
`100.00
`
`Acephate 75% Granules with above composition can be
`prepared by following the process described in EXAMPLE
`1.
`
`EXAMPLE 7
`
`Acephate 50% Granules can be prepared as follows:
`Composition
`
`Ingredients
`
`Quantity (% w/w)
`
`Acephate Technical 98.5% purity
`50.77
`Dispersing agent
`3.00
`Wetting agent
`2.00
`Binding agent
`3.00
`Antifoaming agent
`0.08
`Disintegrating agent
`10.00
`Stabilizer
`1.00
`Filler
`30.15
`Total 100.00
`
`
`
`Acephate 50% Granules with above composition can be
`40 prepared by following the process described in EXAMPLE
`1.
`
`EXAMPLE8
`
`Acephate 40% granules can be prepared as follows:
`45 Composition
`
` Ingredient Quantity (% w/w)
`
`Acephate Technical 98.5% purity
`40.61
`Dispersing agent
`4.50
`Wetting agent
`3.00
`Binding agent
`3.00
`Antifoaming agent
`0.08
`Disintegrating agent
`12.00
`Stabilizer
`1.50
`Filler
`35,31
`
`%9
`
`55
`
`Total
`
`100.00
`
`60
`
` Acephate 40% Granules of above composition can be
`prepared by following the process described in EXAMPLE
`1.
`
`Tests
`
`Acephate 85% granules with above composition can be 65
`prepared by following the process described in EXAMPLE
`1.
`
`The physical properties of Acephate granules were deter-
`mined before and after aging at 45° C. for 500 hrs and for
`flowability, wetting time, attrition test, disintegration rate,
`
`5
`
`

`

`US 6,875,381 B2
`
`7
`tap density, suspensibility, sedimentation and persistent
`foam. No noticeable difference in all the above properties
`wasobserved. The dynamic wetting time and solubility test
`was measured as per MT-167 of CIPAC. The flowability was
`measured as per MJ-172 of CIPAC. The dry sieve analysis
`was measured as per MT-170 of CIPAC. The sedimentation
`was measured as per MT-15.1 of CIPAC. Dustiness of
`granules was measured as per MT-171 of CIPAC. The tap
`density was measured as per MT-58.4 and MT-33 of CIPAC.
`The Acephate technical was determined by the GLC method
`published in AOAC.
`invention has been disclosed in
`Although the present
`terms of a preferred embodiment, it will be understood that
`numerous additional modifications and variations can be
`made without departing from the scope of the invention as
`defined by the following claims.
`Whatis claimed is:
`1. A process for preparing soluble granules comprising
`a) premixing 40 to 98 wt. % an insecticidally active
`compound of the following formula:
`
`R—Y O
`\t
`ppNR'—s
`
`i
`C—R?
`
`R?
`
`wherein R and R? individually are an alkyl, alkenyl or
`alkynyl group containing up to 6 carbon atoms, R? is
`hydrogen, an alkyl group containing 1 to 18 carbon
`atoms, a cycloalkyl group containing 3 to 8 carbon
`atoms, an alkenyl group containing 2 to 18 carbon
`atoms or an alkynyl group containing 3 to 18 carbon
`atoms, R? is hydrogen or an alkyl group containing 1 to
`6 carbon atoms, and Y is oxygenor sulfur;
`0.1-5.0 wt. % a dispersing agent; 0.1-3.0 wt. % a wetting
`agent; 0.1-3.0 wt. % a binding agent; 0.01-0.08 wt. %
`an antifoaming agent; 0.01-10.0 wt. % a disintegrating
`agent; 0.01-1.0 wt. % a stabilizer; and fillers to make
`100 wt. %,
`to form a premix comprising essentially
`95-99% solids and 1-5% moisture and/or solids;
`b) grinding said premix to produce a ground product
`having a predetermined particle size;
`c) post-mixing said ground product to produce a mixture;
`d) granulating said mixture to produce granules;
`e) drying said granules to produce dry granules;
`f) sizing said dry granules to produce sized granules
`having a predetermined length and a predetermined
`diameter; and
`g) sieving said sized granules to separate fines which are
`less than said predetermined length and said predeter-
`mined diameter.
`2. The process of claim 1, wherein said ground product
`has a predetermined particle size of 5—10 microns.
`3. The process of claim 1, wherein said dry granules have
`a predetermined length of 1.5-3.0 mm.
`4. The process of claim 1, wherein said dry granules have
`a predetermined diameter of 0.5 to 1.0 mm.
`5. The process claimed in claim 1, whereinsaid fillers are
`solids in powder form.
`6. The process of claim 1, wherein said binding agentis
`a blend of sucrose and starch derivatives.
`7. The process of claim 1, wherein said wetting agent is
`selected from the group comprising calcium salt of alkyl aryl
`sulphonate and sodium salt of alkyl aryl sulphonate.
`8. The process of claim 1, wherein said dispersing agent
`is a derivative of sulfonated fatty alcohol.
`
`8
`9. The process of claim 1, wherein said disintegrating
`agent
`is a swelling type clay selected from the group
`comprising bentonite and zeolite.
`10. The process of claim 1, wherein said antifoaming
`agentis silicon oil derivative.
`11. The process of claim 1, wherein said stabilizer is a salt
`of a higher fatty acid.
`12. The process of claim 1, wherein said fillers are
`selected from the group comprising precipitated silica and
`kaoline.
`
`13. The process of claim 1, wherein said granulation is
`accomplished by passing said mixture through an orifice
`having and inlet and an outlet.
`14. The process of claim 13, wherein said inlet has a
`temperature of 30-35° C.
`15. The process of claim 13, wherein said outlet has a
`temperature of 40—-45° C.
`16. The process of claim 1, wherein said drying is
`accomplished by passing said granules though an air cham-
`ber.
`17. The process of claim 1, wherein said grinding is
`accomplished by a microniser.
`18. The process of claim 1, wherein said sizing is accom-
`plished by an oscillating cutter.
`19. The process of claim 1, wherein said insecticidally
`active compound is acephate.
`20. The process of claim 1, further comprising;
`h) recycling said fines into step d).
`21. The process of claim 20, wherein said insecticidally
`active compound is acephate.
`22. The process of claim 21, wherein said ground product
`has a predetermined particle size of 5-10 microns.
`23. The process of claim 22, wherein said dry granules
`have a predetermined length of 1.5—3.0 mm anda predeter-
`mined diameter of 0.5 to 1.0 mm.
`24. The process of claim 23, wherein said binding agent
`is a blend of sucrose and starch derivatives.
`25. The process of claim 24, wherein said wetting agent
`is selected from the group comprising calcium salt of alkyl
`aryl sulphonate and sodium salt of alkyl aryl sulphonate.
`26. The process of claim 25, wherein said dispersing agent
`is a derivative of sulfonated fatty alcohol.
`27. The process of claim 26, wherein said disintegrating
`agent
`is a swelling type clay selected from the group
`comprising bentonite and zeolite.
`28. The process of claim 27, wherein said antifoaming
`agent is silicon oil derivative.
`29. The process of claim 28, wherein said stabilizer is a
`salt of a higher fatty acid.
`30. The process of claim 29, wherein said fillers are
`selected from the group comprising precipitated silica and
`kaoline.
`31. The process of claim 20, wherein said granulation is
`accomplished by passing said mixture through an orifice
`having and inlet and an outlet.
`32. The process of claim 31, wherein said inlet has a
`temperature of 30-35° C. and said outlet has a temperature
`of 40-45° C.
`33. The process of claim 32, wherein said drying is
`accomplished by passing said granules though an air cham-
`ber.
`34. The process of claim 33, wherein said grinding is
`accomplished by a microniser.
`35. The process of claim 34, wherein said sizing is
`accomplished by an oscillating cutter.
`36. A process for preparing soluble granules comprising
`a) preparing a dry premix by premixing 40 to 98 wt. % an
`insecticidally active compound of the following for-
`mula:
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`6
`
`

`

`I
`C—R?
`
`R—yY 9
`\tP—N
`
`10
`53. The process of claim 36, wherein said dry premix is
`substantially free from water or solvent.
`54. The process of claim 36, wherein said step of prepar-
`ing said dry premix further comprises premixing 0.1-5.0
`wt. % a dispersing agent, 0.1-3.0 wt. % a binding agent,
`0.01-0.08 wt. % an antifoaming agent, 0.01-10 wt. % a
`R?
`Ris
`disintegrating agent, 0.01-1.0 wt. %astabilizer.
`55. The process of claim 54, wherein said insecticidally
`wherein R and R* individually are an alkyl, alkenyl or
`active compound is acephate.
`alkynyl group containing up to 6 carbon atoms, R? is
`56. The process of claim 55, wherein said dispersing agent
`hydrogen, an alkyl group containing 1 to 18 carbon
`is a derivative of sulfonated fatty alcohol, said binding agent
`atoms, a cycloalkyl group containing 3 to 8 carbon
`is a blend of socrose and starch derivatives,said antifoaming
`atoms, an alkenyl group containing 2 to 18 carbon
`agent is a silicon oil derivative, said disintegrating agent is
`atoms or an alkynyl group containing 3 to 18 carbon
`selected from the group comprising bentonite and zeolite,
`atoms, R? is hydrogen or an alkyl group containing 1 to
`and said stabilizer is a salt of a higher fatty acid.
`6 carbon atoms, and Y is oxygenor sulfur;
`57. The process of claim 56, wherein said dry premix is
`0.1-3.0 wt. % a wetting agent andafiller to make 100
`substantially free of water or solvent.
`wt. %;
`58. The process of claim 54, wherein said dry premix is
`b) grinding said dry premix to produce a ground product
`substantially free of water or solvent.
`having a predeterminedparticle size;
`59. A process for preparing soluble granules consisting
`c) post-mixing said ground product to produce a mixture;
`essentially,
`d) granulating said mixture to produce granules;
`a) preparing a dry premix by premixing 40 to 98 wt. % an
`e) drying said granules to produce dry granules;
`insecticidally active compound of the following for-
`f) sizing said dry granules to produce granules having a
`mula:
`predetermined length and a predetermined diameter;
`and
`
`US 6,875,381 B2
`
`10
`
`15
`
`20
`
`25
`
`Oo
`
`g) sieving said sized granules to separate fines which are
`less than said predetermined length and said predeter-
`mined diameter.
`37. The process of claim 36, wherein said wetting agent
`is selected from the group comprising calcium salt of alkyl
`aryl sulphonate and sodium salt of alkyl aryl sulphonate.
`38. The process of claim 36, wherein said filler is selected
`wherein R and R? individually are an alkyl, alkenyl or
`from the group comprising precipitated silica and kaoline.
`alkynyl group containing up to 6 carbon atoms, R? is
`39. The process of claim 38, wherein said wetting agent
`hydrogen, an alkyl group containing 1 to 18 carbon
`is selected from the group comprising calcium salt of alkyl
`atoms, a cycloalkyl group containing 3 to 8 carbon
`aryl sulphonate and sodium salt of alkyl aryl sulphonate.
`atoms, an alkenyl group containing 2 to 18 carbon
`40. The process of claim 36, wherein said step of prepar-
`atoms or an alkynyl group containing 3 to 18 carbon
`ing said dry premix further comprises premixing 0.1—-5.0
`atoms, R* is hydrogenor an alkyl group containing 1 to
`wt. % a dispersing agent.
`6 carbon atoms, and Y is oxygen or sulfur;
`41. The process of claim 40, wherein said dispersing agent
`0.1-5.0 wt. % a dispersing agent; 0.1-3.0 wt. % a wetting
`is a derivative of sulfonated fatty alcohol.
`42. The process of claim 36, wherein said step of prepar-
`agent; 0.1-3.0 wt. % a binding agent; 0.01-0.08 wt. %
`ing said dry premix further comprises premixing 0.1-3.0
`an antifoaming agent; 0.01-10.0 wt. % a disintegrating
`wt. % a binding agent.
`agent; 0.01-1.0 wt. % a stabilizer; andafiller to make
`45
`43. The process of claim 42, wherein said binding agent
`100 wt. %;
`is a blend of sucrose and starch derivatives.
`b) grinding said dry premix to produce a ground product
`44. The process of claim 36, wherein said step of prepar-
`having a predetermined particle size;
`ing said dry premix further comprises premixing 0.01—0.08
`c) post-mixing said ground product to produce a mixture;
`wt. % an antifoaming agent.
`45. The process of claim 44, wherein said antifoaming
`d) granulating said mixture to produce granules;
`agent is a silicon oil derivative.
`e) drying said granules to produce dry granules;
`46. The process of claim 36, wherein said step of prepar-
`f) sizing said dry granules to produce granules having a
`ing said dry premix further comprises premixing 0.01-10
`predetermined length and a predetermined diameter;
`wt. % a disintegrating agent.
`and
`47. The process of claim 46, wherein said disintegrating
`agent
`is a swelling type clay selected from the group
`comprising bentonite and zeolite.
`48. The process of claim 36, wherein said step of prepar-
`ing said dry premix further comprises premixing 0.01-1.0
`wt. % a stabilizer.
`49. The process of claim 48, wherein said stabilizer is a
`salt of a higher fatty acid.
`50. The process of claim 36, wherein said insecticidally
`active compound is acephate.
`51. The process of claim 36, further comprising;
`h) recycling said fines into step d).
`52. The process of claim 51, wherein said insecticidally
`active compound is acephate.
`
`60. The process of claim 59, wherein said binding agent
`is a blend of sucrose and starch derivatives.
`61. The process of claim 59, wherein said wetting agent
`is selected from the group comprising calcium salt of alkyl
`aryl sulphonate and sodium salt of alkyl aryl sulphonate.
`62. The process of claim 59, wherein said dispersing agent
`is a derivative of sulfonated fatty alcohol.
`63. The process of claim 59, wherein said disintegrating
`agent
`is a swelling type clay selected from the group
`comprising bentonite and zeolite.
`
`R—yY 9°
`\tP—N
`
`C—R?
`
`Ris
`
`R
`
`g) sieving said sized granules to separate fines which are
`less than said predetermined length and said predeter-
`mined diameter.
`
`30
`
`35
`
`40
`
`50
`
`55
`
`60
`
`65
`
`7
`
`

`

`US 6,875,381 B2
`
`11
`64. The process of claim 59, wherein said antifoaming
`agent is silicon oil derivative.
`65. The process of claim 59, wherein said stabilizer is a
`salt of a higher fatty acid.
`66. The process of claim 59, wherein saidfiller is selected
`from the group comprising precipitated silica and kaoline.
`
`12
`67. The process of claim 59, wherein said insecticidally
`active compound is acephate.
`68. The process of claim 59, wherein said dry premix is
`substantially free of water or solvent.
`
`*
`
`ok oR &
`
`8
`
`