CA2210646C - Detergent composition comprising zeolite map and amylase enzymes - Google Patents

Abstract

A detergent composition is disclosed which contains an amylase enzyme, and a detergency builder comprising zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP). Granular and liquid detergent compositions are preferred and methods of making such compositions are disclosed.

Description

DETERGENT COMPOSITION COMPRISING ZEOLITE MAP AND AMYLASE ENZYMES
The present invention relates to a detergent composition comprising an amylase enzyme and a zeolite component as a sequestering agent for water hardness.
Conventionally, water soluble inorganic phosphates, such as sodium tripolyphosphate, have been used as builders far laundry detergents.
More recently, allcali metal aluminosilicate ion-exchangers, particularly crystalline water insoluble sodium aluminosilicate zeolites, have been proposed as replacements for the inorganic phosphates.
For example, EP 21 491A (Procter & Gamble) discloses detergent compositions containing a builder system whicl:l includes zeolite A, X
or P (B) or a mixture thereof. EP 384070A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafl:er referred to as zeolite MAP) and describes their use as detergency builders.
The Applicants have now surprisingly found that a problem may occur when water insoluble zeolite MAP, particularly when present as particles having a small particle size, is used as a detergency builder in a composition not containing amylase enzyme formulated for use in the laundering of fabrics. The choice of a small particle size for any zeolite MAP component, that is to say particles having a particle size, measured as a d50 value, of up to 1.0 micrometres has previously been taught to be preferred in the art, as represented, for example, by EP
384070 A.
The problem relates to the formation of white residues, which adhere to the fabrics and remain thereon at the end of a laundry washing process. The degree of residue formation may vary. On coloured fabrics the appearance of the white residues tends to be visually more apparent than on white fabrics. White residues frequently form on areas of fabric where there is a stain present, interfering with and preventing the complete removal of the stain. As a result of the visible contrast between the white residues and the colowed fabric, the stained area on which white deposits have formed may be more noticeable that the original stain.
It has been established that when an amylase enzyme is employed in compostions containing zeolite MAP, even when in small particle size form, that the problem of the white residue formation on the fabrics is reduced.
It has also been established that the choice of a zeolite having a larger particle size than that taught as preferred by the art, particularly EP 384070A, can further reduce the tendency for the white deposit formation to occur.
Whilst the prior art, as represented for example by European Patent Aplications, EP 384070 A, EP 448297 A, EP 522726 A, EP 533392 A, EP-544492 A, EP 552053 A, and EP 552054 A has envisaged the use of enzymes in combination with zeolite MAP in laundry detergent compositions, none of these prior art documents specifically disclose the use of amylase enzyme with a zeolite MAP component. Furthermore, none of these prior art documents provides any teaching relating to the white residue deposit problem addressed by the current invention, nor of any solution thereto involving the selection of a particular enzyme.
According to the present invention there is provided a detergent composition containing (a) a zeolite builder comprising zeolite P having a silicon to aluminium ratio of not greater than I .33 (zeolite MAP) (b) an amylase enzyme , Detailed descn~tion of the invention Zeolite MAP builder The first essential component of the present invention is a zeolite MAP

WO 96/21718 PCTlUS96100284 builder, optionally in conjunction with one or more supplementary builders.
The zeolite MAP is typically present at a level of from 1 % to 80%, more preferably from 15% to 40% by weight of the compositions.
Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
Zeolite P having a Si:AI ratio of 1.33 or less may be prepared by the following steps:
(i) mixing together a sodium aluminate having a mole ratio Na20:A1203 within the range of from 1.4 to 2.0 and a sodium silicate having a mole ratio Si02:Na20 within the range of from 0.8 to 3.4 with vigorous stirring at a temperature within the range of from 25°C to boiling point usually 95°C, to give a gel having the following composition; A1203: (1.75-3.5) Si02 : (2.3-7.5) Na20 :P
(80-450)H20;
(ii) ageing the gel composition for 0.5 to 10 hours, preferably 2 to 5 hours, at a temperature within the range of from 70°C to boiling point, usually to 95°C, with sufficient stirring to maintain any solids present in suspension;
(iii) separating the crystalline sodium aluminosilicate thus formed, washing to a pH within the range of from 10 to 12.5, and drying, preferably at a temperature not exceeding 150°C, to a moisture content of not less than 5 wt.%.

Preferred drying methods are spray-drying and flash drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity of the product under certain circumstances.
Commercial sodium metasilicate pentahydrate dissolved in water and commercial sodium silicate solution (waterglass) are both suitable silica sources for the production of zeolite P in accordance with the invention. The reactants may be added together in any order either rapidly or slowly. Rapid addition at ambient temperature, and slow addition at elevated temperature (90-95°C) both give the desired product.
Vigorous stirring of the gel during the addition of the reactants, and at least moderate stirring during the subsequent ageing step, however, appear to be essential for the formation of pure zeolite P. In the absence of stirring, various mixtures of crystalline and amorphous materials may be obtained.
Zeolite MAP generally has a calcium binding capacity of at least 150 mg Ca0 per g of anhydrous aluminosilcate, as measured by the standard method described in GB 1473201 (Henkel). The calcium binding capacity is normally 160 mg Ca0/g and may be as high 170 mg Ca0/g.
Although zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.
The amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.
In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.

The dsp value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing dsp values are disclosed in EP 384070A.
Amylase The second essential component of the compositions is an amylase enzyme, that is to say an enzyme having amylolytic activity.
The amylase enzyme is typically incorporated into the compositions in accordance with the invention at a level of from 0.01% to 5%, preferably ~Frnm (1 1 °/ tn ~°/ mnra rvrafPral~lv frnm (1 7°/" tn '7°/., mnet r~rPfPrahlv ft'nm uvui v.i iv w r iv, uavav jravivacava~ uvau v.viv vv viv, auvwr r~vw.».~~J
0.3% to 1.5% active enzyme by weight of the composition, on a 60KNU/g (Kilo Novo Units/gram) activity basis.
The units of 'Kilo Novo Units/gram (I~NU/g)' are a well known means of defining amylolytic enzyme activity and are described in GB-1,269,839 A
(Novo). In more detail, 1 KNU is the amount of enzyme which breaks down 5.25 grams of starch (Merck, Amylum Solubile Erg. B.6, Batch 9947275) per hour in the method described in GB-1,269,839 A, which has the following standard conditions:
Substrate Soluble starch Calcium content in solvent 0.0043 M
Reaction time 'J-20 minutes Temperature 37°C
pH 5.6 The amylase enzyme may be fungal or bacterial in origin. Amylases obtained by chemical or genetic manipulation of fungal or bacterial derived strains are also useful herein. The amylase enzyme is preferably an a-amylase.
Preferred amylases include, for example, a-amylases obtained from a special strain of B. licheniformis, described in more detail in GB-1,269,839 A. Reported deposit numbers for B. licheniformis strains capable of producing a-amylases include NCIB 8061, NCIB 8059, ATCC 6634, ATCC 6598, ATCC 11945, ATCC 8480 and ATCC 9945a.
Preferred commercially available a-amylases include for example, those sold under the trademarks Rapidase and Maxamyl by Gist-Brocades; those sold under the trademark Tea-Theim L-340 by Miles Laboratories, Ellchart, Indiana; those sold under the trademark Rohalase AT by Rohm and Haas, West Philadelphia, PA; and those sold under the trademarks Termamyl 60T and 120T, Fungamyl and BAN by Novo Industries A/S.
In a preferred aspect, the amylases have been designed to have improved stability, particularly having improved stability to oxidation, for example in a bleaching environment, and improved thermal stability. Stability can be measured using any of the technical tests la~own in the art including those referred to in WO 94/02597 A. Stability-enhanced amylases are commercially available from Novo Industries A/S or from Genencor International.
Highly preferred amylases with enhanced oxidative stability are derived using site-directed mutagenesis from one or more of the Bacillus amylases, especialy the Bacillus a=amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Preferred amylases. of this type are described in WO 94/02597 A, and comprise a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis a-amylase, sold under the trademark T~amyl, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B.subtilis, or B.stearothermophilus.
Other preferred amylases having enhanced oxidative stability, derived from B.licheniformis NCIB806, are described by Gencncor International in a paper entitled "Oxidatively Resistant a-Amylases" which was presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant.
Other preferred amylases having enhanced oxidative stability include those described in WO 94/18314 A (Genencor International) and WO 94/02597 A
(Novo). Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other enzyme modifications are acceptable including those described in WO 95/09909 A
(Novo).
It will be appreciated that enzymes for incorporation into solid detergent compositions are generally sold commercially as enzyme prills containing active enzyme supported on a variety of inert host materials, which for example, can include alkali metal sulfates, carbonates and silicates.
Optionally, organic binder materials are also incorporated. In a preferred aspect, the calcium content of these enzyme prills is minimzed to ensure good in-product storage stability of the enzyme.
Additional detergent components The detergent composition according to the invention may contain other detergent components such as surfactants, cobuilders, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
Surfactant The detergent composition according to the invention preferably includes a surfactant selected from avionics, nonionics, zwitterionics, ampholytics and cationics.
The surfactant is preferably present in the detergent compositions at a level of from 1% to 50%, preferably from 3% to 30%, most preferably from 5%
to 20% by weight of the compositions.

WO 96!21718 PCT/L1S96/00284 Many suitable detergent-active compounds are available and fully described in the literature (for example "Surface Active Agents and Detergents" Volumes I and II by Schwartz, Perry and Berch).
Examples of suitable additional anionic surfactants include anionic sulfates, olefin sulphonates, alkyl xylene sulphonates, dialkylsulphosuccinates, and fatty acid ester sulphonates. Sodium salts are generally preferred.
Anionic sulfate surfactant Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the CS-C 1 ~ acyl-N-(C 1-C4 alkyl) and N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C6-C 1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C6-C 1 g alkyl sulfate which has been ethoxylated with from 0.5 to 20, preferably from 0.5 to 5, moles of ethylene oxide per molecule.
Anionic sulfonate surfactant Anionic sulfonate surfactants suitable for use herein include the salts of CS-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 P~~3' or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Nonionic surfactant The nonionic surfactant is preferably a hydrophobic nonionic PCTlUS96100284 surfactant, particularly an alkoxylated nonionic surfactant, having a hydrophilic lipophilic balance (hlb) value of < 9.5, more preferably < 10.5.
Examples of suitable hydrophobic alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of less than 5 alkylene oxide groups per molecule.
The alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.

Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula:
R-O-(CnH2n0)YH
wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or 3.
Preferred nonionic surfactants include prima'y C 11-C 15 ~Phatic alcohols condensed with an average of no more than fve ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, preferably from 25% to less than 50% by weight.
A particularly preferred aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.
Specific examples of suitable alkoxylated adducts of fariy alcohols are Synperonic A3 (ex ICI), which is a C 13-C 15 alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3E0.
Another class of nonionic sufactants comprises alkyl polyglucoside compounds of general formula RO(CnH2nO~Zx wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50%
short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are disclosed in Eh-B 0070074, 0070077, 0075996 and 0094118.

Cobuilders In addition to zeolite MAP, the builder system may contain an organic or inorganic cobuilder.
Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or malefic acids in neutralised form. Suitable inorganic cobuilders include carbonates and amorphous and crystalline layered silicates.
Suitable crystalline layered silicates have the composition:
NaMSix02x+1 . yH20 where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20. Such materials are described in US Patents No. 4664839; No. 4728443 and. No. 4820439 (Hoechst AG). Especially preferred are compounds in which x = 2 and y = O.
The synthetic material is commercially available from Hoechst AG as 8 Na2 Si205 (SKS6) and is described in US Patent No. 4664830.
The total amount of detergency builder in the granular composition typically ranges from 10 to 80 wt.%, more preferably from 15 to 60 wt% and most preferably from 10 to 45 wt.%.
Bleach Detergent compositions according to the invention may also suitably contain a bleach system. This preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
The bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a peroxyacid bleach precursor. Suitable persalts include sodium perborate monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being most preferred.
Preferred bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors.
Physical form The detergent composition according to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositions are preferred.
Making process The detergent compositions of the invention may be prepared by any suitable method. The particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.
In processes based around a spray-drying tower, a base powder is first prepared by spray-drying a slurry and then other components unsuitable for processing via the slurry can be sprayed on or admixed (postdosed).
The zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be incorporated post-tower. The crystalline layered silicate, where this is employed, is also incorporated via a non-tower process and is preferably postdosed.
Alternatively, particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as granulation.
The granular detergent compositions of the invention may be prepared to any suitable bulk density. The compositions preferably have a bulk density of at least 400 g/1 preferably at least 550 g/1, most preferably at least 700 g/1 and, with particular preference at least 800 g/1.

The benefits of the present invention are particularly evident in powders of high bulk density, for example, of 700 g/1 or above. Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
The detergent composition of the invention may be formulated as a liquid detergent composition which may be aqueous or anhydrous. The term "liquid" used herein includes pasty viscous formulations such as gels. The liquid detergent composition generally has a pH of from 6.5 to 10.5.
The total amount of detergency builder in the liquid composition is preferably from 5 to 70% of the total liquid composition.
Illustrative compositions according to the present invention are presented in the following Examples.

In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS : C 11-C 13 ~e~' ~'1 benzene sulfonate K
45AS : Branched sodium alkyl sulfate surfactant containing C 14-C :l 5 ~yl chains 246AS : Sodium alkyl sulfate surfactant containing a alkyl chain length weight distribution of 15% C12 alkyl chains, 45% C14 alkyl chains, 35% C16 alkyl chains, 5% C 1 g alkyl chains TAS : Sodium alkyl sulfate surfactant containing predominantly C 1 ~ - C 1 g alkyl chains derived from tallow oil.
24AE3 S : C 12-C 14 ~yl etlaoxysulfate containing an average of three ethoxy groups per mole 35E3 . A C13-15 P~~3'' ~eohol condensed with an average of 3 moles of ethylene oxide 25E3 . A C12-C15 P~~'Y ~cohol condensed with an average of 3 moles of ethylene oxide .
24EY . A C12-14 l~e~' p~~'Y ~cohol condensed with an average of Y moles of ethylene oxide Citrate : Sodium citrate Carbonate . Anhydrous sodium carbonate Perborate . Sodium perborate tetrahydrate r Percarbonate . Sodium percarbonate TAED : Tetra acetyl ethylene diamine Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio normally follows) CMC : Carboxymethylcellulose Suds : 25% para~n wax Mpt 50°C, 17%
Suppressor hydrophobic silica, 58% paraffn oil Zeolite MAP : Hydrated sodium aluminosilicate zeolite MAP
having a silicon to aluminium ratio of 1.07 MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000.
Amylase : Amylolytic enzyme sold under the trademark Termamyl 60T by Novo Industries A/S
(60KNU/gram enzyme activitiy) BSA : Amylolytic enzyme - M197T variant, having enhanced oxidative stability (60KNU/gram enzyme activity) Protease : Proteolytic enzyme sold by Novo Industries A/S
under the trademark Savinase of activity 4.0 KNPU/gram.
Lipase : Lipolytic enzyme sold by Novo Industries A/S
under the trademark Lipolase of activity 100,000 LU/gram Example 1 The following granular laundry detergent compositions were prepared (parts by weight) in accordance with the invention. All amylase enzyme levels relate to levels of active enzyme, expressed on a 60 KNUIg activity basis.
A B C D E

246AS 7.6 6.5 4.8 6.8 -TAS - - - 8.6 24AE3 S 2.4 - 1.2 1.7 25E3 3.26 - - - 6.3 35E3 - 5.0 5.0 5.0 -Zeolite MAP 20.0 25.0 20.0 25.0 31.0 Carbonate 15.0 15.0 20.0 10.0 12.0 MA/AA 4.25 4.25 4.25 4.25 2.0 Perborate - 16.0 - 16.0 20.0 Percarbonate 20.0 - 20.0 - -TAED 5.0 5.0 5.0 5.0 6.7 Am lase 0.2 0.5 - 0.1 0.1 BSA - - 0.2 - -Protease 0.04 0.08 - 0.05 0.05 Silicate (2.04.0 - - 4.0 3.0 ratio Water and miscellaneous (Including suds suppressor, sodium sulphate, perfume) to balance Example 2 The following granular laundry detergent compositions of density 850 gram/litre are prepared (parts by weight) in accordance with the invention.
All amylase levels relate to levels of active enzyme, expressed on a 60 KNU/g activity basis.
F G H I J

45AS 9.0 8.5 9.5 9.0 6.0 LAS - - - - 3.0 24E3 2.8 2.9 3.0 2.8 2.8 24E5 6.5 6.4 6.5 6.2 6.5 Zeolite MAP 32.0 35.0 25.0 - 16.0 Zeolite A - - - 30.0 15.0 Citrate 3.3 3.0 3.5 3.5 3.0 Carbonate 9.0 9.0 9.0 '10.0 12.0 MA/AA - _ _ - 2.0 CMC 0.8 0.5 0.8 1.0 0.8 Perborate - - - - 16.0 Percarbonate 20.0 18.0 20.0 22.0 -TAED 4.7 4.7 4.7 4.7 4.7 Am lase ~ O.I 0.3 - 0.5 0.2 BSA - - 0.4 - -Protease 2.4 2.0 1.5 2.0 1.0 Li ase 0.35 0.35 0.4 0.3 0.2 Silicate (1.6S.l 6.0 4.5 5.0 5.0 ratio Water and miscellaneous (Including suds suppressor, sodium sulphate, perfume) to balance

Claims (13)

1. A detergent composition containing (a) a zeolite builder comprising zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP) (b) an amylase enzyme.

2. A detergent composition according to Claim 1 wherein said zeolite MAP builder has a particle size, expressed as a d50 value of from 1.0 to 10.0 micrometres.

3. A detergent composition according to Claim 2 wherein said zeolite MAP builder has a particle size, expressed as a d50 value of from 2.0 to 7.0 micrometres.

4. A detergent composition according to Claim 1 wherein said zeolite builder is present at a level of from 1% to 80% by weight of the composition

5. A detergent composition according to Claim 1 wherein said amylase enzyme is an .alpha.-amylase.

6. A detergent composition according to Claim 1 wherein said amylase enzyme has been modified such as to enhance its oxidative stability.

7. A detergent composition according to Claim 1 wherein said amylase enzyme is present at a level of from 0.01% to 5%, active enzyme by weight of the composition, on a 60 KNU/g activity basis.

8. A detergent composition according to Claim 1 wherein said amylase enzyme is present at a level of from 0.2% to 2%

active enzyme by weight of the composition on a 60 KNU/g activity basis.

9. A detergent composition according to Claim 1 containing a surfactant at a level of from 1% to 50% by weight of the composition.

10. A detergent composition according to Claim 1 to containing an organic or inorganic cobuilder.

11. A detergent composition according to Claim 10 wherein said cobuilder is a crystalline layered silicate.

12. A detergent composition according to Claim 1 containing a bleach system comprising a peroxy bleach compound and a peroxyacid bleach precursor.

13. A detergent composition according to Claim 12 wherein said peroxy bleach compound is sodium percarbonate.