FR2539427A1 - DETERGENT SOFTENING COMPOSITIONS - Google Patents

Abstract

THE PRESENT INVENTION PROVIDES PARTICULAR DETERGENT COMPOSITIONS OF HIGH ACTIVITY, PARTICULARLY FOR GIVING BETTER PROPERTIES AND DETERSITIVE EFFECTS TO WASHED TISSUES WITH SAID COMPOSITION, THIS COMPOSITION INCLUDING, IN ADDITION TO A CLASSIC ADDITIVE AND A TENSITIVE MAINLY ANIONIC, A CATIONIC SOFTENER IN PARTICLES OF THE TYPE (LOWER DIALKYL) - (SUPERIOR DIALKYL) - QUATERNARY AMMON AND / OR OF THE HETEROCYCLIC IMIDE TYPE, FOR EXAMPLE IMIDAZOLINIUM, A MIXTURE OF NON-ION ACTIVE INGREDIENT FAT AND NON-IONIC ORGANIC SURFACTANT, THE RATIO BY WEIGHT OF SOAP TO SOFTENER IS APPROXIMATELY 8: 1 TO 1: 3, PREFERABLY FROM 5: 1 TO 1: 2, AND BETTER THAN 3: 2 AT 2: 3, FOR EXAMPLE ABOUT THE UNIT. THE NON-IONIC SOAP-SURFACTANT-SOAP MIXTURE AS WELL AS THE CATIONIC SOFTENER-NON-IONIC AGENT MIXTURE ARE IN THE FORM OF SPAGHETTI, FLAKES OR OTHER FORMS AND ARE PRESENT IN THE FORM OF DISPERSED DISENGENTLY SENSITIVE PARTICLES. THE INVENTION ALSO DESCRIBES A PROCESS FOR WHITENING TISSUES USING THE ABOVE-MENTIONED COMPOSITION.

Description

The present invention relates to compositions

  detergents and in particular detergent compositions-

  softeners capable of imparting greater flexibility, detergent effects, anti-redeposition-soiling and anti-static properties to the fabrics treated with them, and

  in particular in a machine laundering operation.

  The detergent compositions of the present invention are also remarkable in that they produce less greasy stains (due to the cationic softener)

  on washed and dried clothes.

  The compositions intended to ensure simultaneous-

  a detergent effect and an appreciable degree of flexibility in machine washing of fabrics, and therefore suitable for use in the washing cycle, are well known and widely available commercially. The brief interaction

  between the anionic surfactant, perhaps the most common

  used available types of surfactants, and

  cationic softeners, especially those of the dial- type

  kyl (lower) dialkyl (upper) quaternary ammonium, is

  also well established in the patent literature.

  This interaction often results in the formation of unsightly precipitates which are trapped in the tissue

  washed or otherwise deposited on the fabric A

  coloring or other unpleasant unsightly effects are

  for the most part inevitable It often results

  wind a decrease in the effective amount of anionic available for useful purposes because the loss of anionic is

the main consequence.

  The techniques proposed so far to solve the above problem of the interaction between cationic-anionic agents, although differing in their mode

  seem to converge with regard to the results

  tats, i.e. they leave something to be desired Thus, although the most effective types of cationic softeners of the quaternary ammonium type, examples of which are 2539 t 27

  compounds mentioned above of quaternary ammonium of the dial- type

  higher kyle, for example distearyl dimer chloride

  thyl ammonium, can act in the washing cycle by pre-

  sence of anionics, additives, etc., the quantity required to obtain the desired softening is generally close to

  amounts favoring unwanted cationic interaction-

  anionics As a rule, the amount of catio-

  picnic is about double that required for

  obtain a softening effect as for an antistatic effect

  than. In the patent of the United States of America NO.3 325 414 mainly concerning detergents with foam or controlled clarity, the problem of the cationic-anionic interaction and the associated harmful effects are described in detail. The patent also points out that certain compounds of quaternary ammonium, among the class of cationic agents, are generally unstable when heated and when in contact with alkaline additives, instability manifested by the release of strong amine odors and an undesirable color The compositions of this patent are limited to the use of halides

  of quaternary ammonium having only one al-

  higher kyle, the structural formula given for the compound

  cationic being correspondingly limited The com-

  cationic poses of this type are significantly lower than the higher dialkyl types at least as far as

  the softening action of the tissues.

  Other teachings of the prior art obviously

  at least tactically attempt the use of cationic softeners while proposing the use, for example, of anionic materials as softeners.

  U.S. Patent No. 3,676,338 is shown

  and describes the use of an anionic softener known as "branched chain carboxylic acids" as

  fabric softener It is assumed that an anio-

2539427 i

  pic would be stable in the presence of the anionic softener.

  According to the above, the solutions proposed require the rejection of softeners and mainly of

  those of the dialkyl (upper) dialkyl (lower) salt types -

  quaternary ammonium and cyclic imide, these having been considered by experience as being among the most effective softeners having been developed so far

in practice.

  The problem of the incompatibility of the cationic in anionic detergents is also known from the US Pat. Nos. 3,936,537 and NO 4,141,841 which propose to use, as an essential ingredient in combination with the cationic substance, a

  organic dispersion inhibitor An im-

  bearing these inhibitors is maximum solubility in

  water at 250 C at 50 ppm Similar descriptions may

  also be found in United States Patent Nos. 4,113,630, No. 4,196,104 and No. 4,272,386 In United States Patent No. 4,230,590, there is described

  very powerful detergents including a conventional additive

  that mainly anionic surfactants

  a cationic softener and a mixture of acid soap

  fat and cellulose ether The mixture of soap and cellulose ether is in the form of spaghetti, flakes or other form and is present in the composition

  as discrete particles dispersed sensibly

so homogeneously.

  U.S. Patent No. 4,298,480 describes very powerful detergents having a composition

  similar to that described in the previous paragraph in the ex-

ception of cellulose ether.

  U.S. Patent No. 4,329,237 describes very powerful detergents also analogous to

  those of the two preceding paragraphs, except that the parts

  soap capsules are mixed with a non-io- surfactant

fuck.

  Although the above-mentioned detergent compositions

  containing a cationic soap and softener

  try advantageous softening and detersive properties, it has been found that an optimal softener without formation of

stains could not be obtained.

  The present invention provides stable detergent softener compositions capable of improving the

  flexibility without staining and providing better

  their properties of detergent, anti-static and anti-

  redeposition of dirt on fabrics treated with them during a laundering operation in cold or hot water The compositions generally comprise, by weight, approximately from 5 to 40% of an anionic surfactant without

  soap, water-soluble, about 10 to 60% of additive salt hy-

  soluble to neutral to alkaline, about 2 to 20% of a softener

  cationic cissant chosen from (a) aliphatic salts of di- (lower C 1 -C 4 alkyl), di- (higher alkyl

  C 14-C 24) quaternary ammonium, (b) heterocyclic compounds

  and mixtures of (a) and (b), said cationic agent

  being in intimate mixture with a nonionic hydroso- compound

  luble (2 to 50% by weight relative to the cationic component),

  and about 0-20% of a soap fatty acid soap mixture

  water-soluble or dispersible and a nonionic organic surfactant in the form of spaghetti, or other discrete form,

  the weight ratio of soap (if used) to softener

  sant being about 2: 3 to 3: 2, the percentage of concentra-

  tion of the anionic surfactant being at least about 1.5 x

  + 5, x representing the percentage of concentration of the additive

  waxing, the soap being dispersed in a substantially homogeneous manner

  gene throughout said composition, preferably

  as discrete particles.

  In the non-ionic soap-surfactant mixture,

  the non-ionic constitutes approximately from 2 to approximately 50%, of pre-

  ference approximately from 5 to approximately 40%, better still approximately from 2539427, l 8 to approximately 30%, and more particularly approximately from 8 to

  about 20%, all the percentages being expressed by weight.

  The total content of non-ionic surfactant in the mixture

  soap ranges from about 0.04% to about 10%, preferably

  from about 0.1% to about 8%, and in particular from about 1.6 to about 6%, and better still from about 1.6% to about 4%, all the percentages being expressed by weight and by

  relative to the weight of the detergent composition.

  In certain other aspects, the invention encompasses both the methods of formulating and using

compositions described above.

  According to the present invention, by adding the ma-

  cationic substance in intimate mixture with the organic surfactant

  non-ionic picnic in flakes, granules, or other form, the

  formation of stains on fabrics after drying is sensitive

  In addition, the flexibility of the washed fabrics is

  generally surprisingly improved The non-ionic surfactant

  that also contributes to the anti-redeposition of soiling,

  especially in the case of phosphate-free formulations.

  The incorporation of the non-organic surfactant

  ionic in the cationic softening composition has the following additional advantages In general, the nonionic surfactants are added afterwards to the

  spray-dried detergent compositions

  quence, the nonionic surfactant added afterwards increases

  In the present invention, the nonionic surfactant is incorporated into the cationic product added afterwards, which ensures

  marked improvement in the fluidity of the deter-

kind.

  In the embodiments of the present invention using soap particles with or without

  cellulose ether or nonionic surfactant, as indicated

  qué in the patents of the United States of America N O 4 230 590, No 4 298 480, No 4 329 237 cited above, useful fatty acids 25394 t 27 i

  generally include those derived from natural fatty acids

  real or synthetic with 10 to 30 carbon atoms

  in the alkyl chain We prefer alkali metal soaps

  lin, for example sodium and / or potassium of Clo-C 24 'saturated fatty acids, a particularly preferred class consisting of the sodium and / or potassium salts of mixtures of fatty acids derived from coconut and tallow, for example the combination of sodium soap, coconut oil and potassium tallow soap, in the proportions

  as of 15/85 As we know, the inhibitory power

  the fatty acid foaming agent is all the more pronounced

  as its molecular weight increases so the choice of acid

  fat in this case can be carried out depending on the desired degree of foaming of the composition In general, one obtains

  effective results when at least about 50% of the sa-

  fatty acid are in category C 10-C 18 Other fatty acid soaps useful here include those derived from ground peanut oil, hardened fish, for example cod and shark liver, seal, perilla, flaxseed, bancoul, hempseed, walnut, poppy, sunflower, corn, rapeseed, mustard seed, apricot kernel, castor oil and d olive, etc. Other fatty acid soaps include those derived from

  following acids: oleic, linoleic, palmitoleic, palm

  tick, linolenic, ricinoleic, capric, myristic, etc., other useful combinations including, without the need to limit, 80/20 capriquelauric, 80/20 capric-myristic, / 50 oleic-capric, 90/10 capricpalmitic, etc. Nonionic surfactants useful in

  soap particles and mixed with cationic agents

  What are known materials? These non-ionic surfactants

  that can be broadly defined as being water-soluble compounds obtained by condensation of alkylene oxide groups (of hydrophilic nature) with a hydrophobic organic compound, which can be of aliphatic or alkyl nature 2539427 i

  aromatic The length of the hydrophilic or polyoxy-

  alkylene which is condensed with any hydrophobic group by-

  particular can be easily adjusted to give a compound

  water soluble having the desired degree of balance between elements

hydrophilic and hydrophobic elements.

  For example, a well-known class of tensio-

  non-ionic organic active ingredients is available on the market

  under the brand name "Pluronic" These compounds are formed by

  densification of ethylene oxide with a hydrophobic base obtained

  by condensation of propylene oxide with propylene-gly-

  col The hydrophobic portion of the molecule which, naturally, has an insolubility in water, has a molecular weight of approximately 1500 to 1800 The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the solubility in water of the molecule as a whole and the liquid character of the product is maintained up to the point where the content of polyoxyethylene radicals is approximately 50% of the total weight

of the condensation product.

  Other suitable nonionic synthetic surfactants include:

  1 Poly-oxide condensation products

  ethylene and alkylphenols, for example the products of

  densification of alkylphenols having an alkyl group of about

  with 6 to 12 carbon atoms in a straight or branched chain configuration, with ethylene oxide, said ethylene oxide being present in amounts of 5 to 25 moles of ethylene oxide per mole of alkylphenol Le alkyl substituent of these compounds can be derived from propylene,

  polymerized diisobutylene, octene or nonene, for example-

  full. 2 Those derived from the condensation of ethylene oxide with the product resulting from the oxide reaction

  of propylene and ethylene diamine For example, the compounds

  containing about 40% to about 80% by weight of po-

  lyoxyethylene and having a molecular weight of about 5000

2539427,

  to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base consisting of the reaction product of ethylenediamine and an excess of

  propylene, said base having a molecular weight of gold-

from 2500 to 3000, are suitable.

  3 The condensation product of alipha-

  ticks having 8 to 30 carbon atoms, in a straight or branched chain configuration, with 2 to 100 moles of ethylene oxide, for example a condensation product of coconut alcohol and ethylene oxide having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms The nonionic surfactants include

  nonylphenol condensed with either about 10 or about 30 mo-

  ethylene oxide per mole of phenol and coconut alcohol condensation products with an average of about, 5 or about 15 moles of ethylene oxide per mole of alcohol, and the condensation product of about 15 moles

  ethylene oxide with one mole of tridecanol.

  Other examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 15 moles of ethylene oxide per mole of phenol; dodecyl-mercaptancondensed with 10

  moles of ethylene oxide per mole of mercaptan; the bis- (N-

  2-hydroxyethyl) lauramide; nonylphenol condensed with 20 moles of ethylene oxide per mole of nonylphenol; myristyl alcohol condensed with 10 moles of ethylene oxide per mole of myristyl alcohol; lauramide condensed with 15

  moles of ethylene oxide per mole of lauramide; and the di-

  isooctylphenol condensed with 15 moles of ethylene oxide.

  Among the nonionic surfactants listed above, the alcohol condensation product is preferred.

  aliphatic of 8 to 22 carbon atoms with the oxide of

  thylene Representative examples of these nonionic surfactants are Neodol 25-7, a product of Shell -9 Chemical Co, which consists of the condensation product of C 12 _ 15 alcohol with 7 moles of oxide ethylene and Neodol 23-6 5 which is the condensation product of an alcohol

  in C 12-13 with 6.5 moles of ethylene oxide.

  The cationic softeners useful here are known materials and are of the high potency type

  softener They include the N, N-di-alkyl (higher

  laughing C 14-C 24), N, N-dialkyl (lower Cl-C 4) ammonium quater-

  naire with anions of solubilization in water such as a halide, for example chloride, bromide and iodide; sulfate, methosulfate, and the like, and imides

  heterocyclics such as imidazolinium salts.

  For convenience, the aliphatic quaternary ammonium salts can be defined by the following structure:

R +

R-N R 2 X

  R 3 in which R and R 1 represent an alkyl group of 14 to 24, and preferably of 14 to 22 carbon atoms; R 2 and R 3 represent a lower alkyl group of 1 to 4, and preferably 1 to 3 carbon atoms, X represents an anion capable of imparting solubility or dispersibility in water including the chloride, bromide, iodide, sulfate and methosulfate mentioned above Particularly preferred species of aliphatic quaternary ammonium compounds include: distearyl dimethylammonium chloride, di- (hydrogenated tallow) dimethylammonium chloride, di- (tallow) dimethylammonium chloride, disteararyl dimethylammonium methyl sulfate ,

  di- (hydrogenated tallow) dimethyl ammonium methyl sulfate.

  Heterocyclic imide softeners of the imidazolinium type can also, for convenience, be defined by the following structure:

-N CH 2 O

R 4 CH 2 CH 2 NH -C R 6 X

  in which R 4 is a lower alkyl group of 1 to 4, and

  preferably from 1 to 3 carbon atoms; R 5 and R 6 represent

  each of the substantially linear upper alkyl groups

  res of about 13 to 23 and preferably 13 to 19 atoms of

  carbon, and X has the above meaning Species per-

  Particularly preferred imidazoliniums include:

  methyl sulfated 1-methyl-1- (tallow) amidoethyl-2- (tallow) -imi-

  dazolinium; commercially available from Sherex Chemical Co under the registered trademark Varisoft 475 in the form of a liquid containing 75% of active material in isopropanol,

  1-methyl-1-oleyl-amido-ethyl-2-oleyl-methyl sulfate

  imidazolinium; commercially available from Sherex Chemical Co, under the registered trademark Varisoft 3960,

  75% active ingredient in isopropanol.

  According to one aspect of the present invention, it is preferable that the soap and the nonionic surfactant

  be used in combination such that soap is used

  read in a quantity at most equal, and preferably less

  less than that of the nonionic surfactant, for example from about 2% to about 50% of the mixture, preferably from about 5% to about 40%, and better still from about 8 to about 30%, and especially about 8 to about

  %, based on the total soap-surfactant mixture not

  ionic to be introduced into the final detergent composition, usually by post-mixing the soap and the cationic agent-nonionic agent mixture with the dried detergent The soap and the nonionic surfactant in the combined state can be mixed first in the desired proportions to form a substantially homogeneous mass which can be worked, according to well known techniques, until it is sufficiently "pasty" or plastic to have a shape suitable for, preferably, extrusion or other process, for example pastillation, granulation,

  stamping and compression Work can be done

  killed, for example, by roller milling, although this is not essential, then extrusion in a extruder at

  classic soap with the desired type of extrusion head.

  The latter is chosen according to the form,

  i.e. the geometric shape desired for the extrudate The ex-

  trusion in the form of spaghetti or noodles is particularly

  Rely preferred Other shapes such as glitter,

  tablets, lozenges, ribbons, threads, and the like, consisting of

  kill suitable variants Special extruders

  for the above applications are well known in practice.

  that and include for example the Elanco EXD-60 models; EXCD-100; EX130 and EXD-180, a Buhler extruder, and the like In general, the spaghetti-shaped extrudate

  is a self-supporting mass, i.e. semi-so-

  smooth and essentially non-sticky at room temperature

  biante not requiring, in most cases, no treatment

  additional drying such as water removal If necessary, this last operation can be carried out by simple drying techniques. The spaghetti must

  have an average length of about 2 to 20 mm, a proportion

  about 95% of them with a tolerance of 0.5 to 20 mm, and an average diameter or width of about 0.2 to 2.0 mm, a range of 0.4 to 0.8 mm being preferred density

  apparent spaghetti which is generally a function of the ty-

  eg fatty acid soap and nonionic surfactant used

  edged, is about 0.9 to 1.3 g / cm The glitter measured

  about 4 mm long and wide and 0.2 mm thick

  thickness, the tablets have a section of 2.5 mm while the tablets have a section of 2.5 mm and a thickness

2.5 mm.

  The cationic compound-nonionic compound mixture

  can be prepared in the same way as the soap-

  non-ionic compound It is however preferable to use

  mixing in the form of tablets The tablets are pro-

  picks by atomization cooling of a liquid mixture

  required for the cationic agent and the nonionic agent In the embodiments which are particularly preferred, a liquid nonionic agent is used (for example the

  Neodol 23-6 5) and added to the molten cationic agent.

  An example of a cationic agent is Arosurf TA-100 (dimethyldistearyl ammonium chloride) and, as supplied, this material forms a very fluid liquid when it is

  melted and heated to 90 ° C. The liquid mixture of catio-

  nique and non-ionic agent can, in another form of

  preferred embodiment, be allowed to cool to room temperature

  ambient or, as required, to solidify. The solid can then be ground to the desired particle size and added afterwards to the other detergent ingredients. In general, we plan to use from 1 to 20%

  by weight of nonionic agent relative to the weight of the softener

  cationic cissant Preferably, the non-ionic agent must be used in proportions of 5 to 15%, a proportion of approximately 10% being particularly preferred in the case

Neodol 23-6 5.

  Although conventional type surfactants can be used here, it is preferable that at least about 90%, and preferably at least about 95% of the

  all of the surfactant or detergent either of the anio- type

  nique, these materials being particularly advantageous in

  detergents with very strong action for washing fabrics.

  Anionic agents to be used here generally include-

  the water-soluble salts of organic reaction products

* nics having in their molecular structure an anionic solubilization group such as a group SO 4 H, 503 H, COOH and PO 4 H and an alkyl group, in particular an alkyl of approximately

  8 to 22 carbon atoms in the alkyl group or fragment.

  Suitable detergents are the anionic detergent salts carrying alkyl substituents of 8 to 22 carbon atoms, for example the water-soluble, sulphated and anionic sulphonated salts of alkali and alkaline earth metals and detergent salts containing a higher alkyl moiety

  hydrophobic such as salts of (higher alkyl) aryl-

  mono or polycyclic sulfonates having from about 8 to 18 carbon atoms in the alkyl group which may have a straight (preferred) or branched chain structure,

  preferred species including, but not limited to, tri-

  sodium linear decylbenzenesulfonate, dodecylbenzene-

  linear sodium sulfonate, sodium decyl-benzene-linear sulfonate, lithium or potassium pentapropylene benzenesulfonate; alkali metal salts of

  sulphated ethylene oxide condensation products,

  for example 3 to 20 and preferably 3 to 10 moles of ethylene oxide, with aliphatic alcohols containing 8 to 18 carbon atoms or with alkylphenols having alkyl groups of 6 to 18 carbon atoms, for example the sodium salt of nonylphenolpentaethoxylated sulfate and the sodium salt of triethoxylated (lauryl alcohol) sulfate; alkali metal salts of saturated alcohols containing

  about 8 to 18 carbon atoms, for example lauryl-

  sodium sulfate and sodium stearyl sulfate; alkali metal salts of higher fatty acid esters of low molecular weight alkylol sulfonic acid, for example

  fatty acid esters of isethionic acid sodium soap

  than; fatty ethanolamide sulfates; fatty acid amides of aminoalkylsulfonic acids, for example lauric acid amide of taurine; alkali metal salts of hydroxy alkane sulfonic acids having 8 to 18 atoms

2539427,

  carbon in the alkyl group, for example hexadecyl-alpha-

  sodium hydroxy sulfonate The anionic agent or the mixtures

  These are used in the form of alkali or alkaline earth metal salts. The anionic agent is preferably of the soap-free type, with the soap component being preferred as described. However, minor amounts of soap , for example up to about%, and preferably 20%, based on the totality of the anionic agent, can be added, for example, in the grinding mixture The concentration of the anionic agent

  soap-free should preferably be chosen to provide

  define an excess compared to the cationic softener according to the empirical relationship:% of concentration = 1.5 x + 5,

  where x is the percentage of concentration of softening

  cationic cissant This ensures the minimum excess of anionic agent necessary for maximum detergent power, softening, etc., of the composition.

  Minor amounts of other types of deter-

  gents can be incorporated at the same time as the anionic agent, their sum, in any case, not exceeding approximately 10% and preferably approximately 2 to 5% of the total detergent, that is to say other detergent plus anionic agent without soap. Particularly interesting are nonionic surfactants which contain a group

  hydrophobic organic and a hydrophilic group which is a pro-

  reaction product of a solubilization group such as car-

  boxylate, hydroxyl, amido or amino with ethylene oxide

  or with its polyhydration product, polyethylene-

  glycol Y include the condensation products of C 8 to C 30 fatty alcohols such as tridecyl alcohol with 3 to moles of ethylene oxide; a C 16 to C 18 alcohol with 11 to 50 moles of ethylene oxide; addition products

  of ethylene oxide on polyhydroxy alcohol monoesters

  lique, for example hexahydroxylic; con- products

  densification of polypropylene glycol with 3 to 100 moles of ethylene oxide; alkyl condensation products (straight or branched chain C 6 to C 20) phenols with 3 to 100 moles

  ethylene oxide, and the like.

  Suitable amphoteric detergents generally include those containing both an anionic group and a cationic group and a hydrophobic organic group which is preferably an aliphatic radical greater than 10 carbon atoms; examples include N-higher alkyl-aminocarboxylic acids and N-higher alkyl-minodicarboxylic acids as described in

  U.S. Patent No. 3,824,189.

  The compositions according to the invention preferably comprise an alkaline to neutral water-soluble additive salt.

  eh proportions of about 10 to 60% by weight of the com-

  total position Additives can be used in this case

  organic and inorganic including the phosphates of

  alkaline and alkaline earth levels, especially phos-

  condensed phates such as pyrophosphates or tripolyphos-

  phates, silicates, borates, carbonates, bicarbonates and si-

  milaires Compounds of this type include tripoly-

  sodium phosphate, trisodium phosphate, pyrophos-

  tetrasodium phate, sodium acid pyrophosphate, sodium monobasic phosphate, sodium dibasic phosphate, sodium hexametaphosphate; alkali metal silicates such as sodium metasilicate,

  sodium silicates: Na 20 / Si O 2 from 1.6: 1 to 3.2: 1, the carbon

  sodium nate, sodium sulfate, borax (tetraborate

  sodium), the tetrasodium salt of ethylenediamine acid-

  tetracetic, trisodium nitrilotriacetate and the like, and mixtures of the above compounds The additive salt can be chosen so as to provide detergents containing phosphates or without phosphates In the latter embodiments, sodium carbonate is particularly

  another material providing good deter-

  tergents is metakaolin which is generally produced by heating a network of kaolinite to expel water by producing a material which is substantially amorphous according to X-ray examination, but which retains part of the

  ordered structure of kaolinite Descriptions of the

  Kaolin and Metakaolin are found in U.S. Patent No. 4,075,280, Columns 3 and 4 and in Grimshaw's book "The Chemistry of Physics of Clays

  and Allied Ceramic Materials "(4th edition, Wiley-Inter-

  science), pages 723-727 Metakaolin is also the subject of patent applications from the United States of America N 905 622

  and N 905 718, the descriptions of which are incorporated here at

  title of reference Metakaolin also seems to have a softening action. As far as it is concerned, the most effective metakaolins seem to be those which have the best behavior in the reaction with sodium hydroxide to form zeolite 4 A as described in the patent. of

  United States of America N 3,114,603 which refers to these ma-

  as a "reactive kaolin" As described in the

  reference sources, metakaolin is an alumino-silicate.

  Metakaolin and / or a zeolite are included in about the same amounts as the additive salt, and preferably in a higher proportion, for example at a ratio of zeolite to silicate of 6: 1. A particularly useful form of metakaolin is commercially available

  under the designation Satintone N 2.

  Useful preferred optional ingredients include fragrances such as Genie fragrance; optical brightening agents and brightening agents which may be dyes or pigments, suitable materials

  in this regard including stilbene and Tinophal 5 BM (mar-

  than deposited) (brightening agents) in particular in combination

  bran and Sky blue direct bright 6 B, Solophenyl violet 4 BL, Cibacete, Blue brilliant RBL, Cibacete violet B, Blue brilliant Polar RAW and Calcocide blue 2 G (agents

2539427,

  brightening agent) The brightening agent can be incorporated in proportions up to about 1% of the total composition while the brightening agents can be present in a proportion reaching about 0.1%, preferably about 0.01% of the total composition The whitening agent, for example "Polar Brilliant Blue", can be incorporated into the soap in the form of spaghetti In either case,

a minimum quantity is sufficient.

  Other optional ingredients include bleaches which may be of the releasing type

  oxygen or chlorine; oxy-based bleaching agents

  genes include sodium and potassium perborate, potassium monopersulfate and the like, while

  chlorinated bleaches are for example the hypo-

  sodium chlorite, potassium dichloroisocyanurate, trichloroisocyanuric acid and the like The last mentioned chlorine bleaching agents

  place are representative examples of the important class

  a lot of dry, organic solid bleaches,

  water-soluble known as N-chloro-imides compre-

  their alkali metal salts These cyclic imides have about 4 to 6 members in the nucleus and are described in

  detail in US Patent No. 3,325,414.

  Each of the oxygenated and chlorinated bleaches

  described above is fully compatible with the

  sitions of the present invention and has good stability in the presence of anionic and cationic components. They are generally used in proportions of between about 0.1 and 45% by weight of the total solids or from about 0.05% to around 40% based on

the total detergent composition.

  Other optional ingredients include a soil suspending agent, cellulosic,

  colloidal, hydrophobic, soluble and / or dispersible in water.

  Methyl cellulose, for example Methocel (registered trademark), is particularly effective Polyvinyl alcohol is also effective and in particular for washing cotton and synthetic fibers for example Nylon, Dacron and cotton treated with a resin The additional soil suspending agent can be incorporated in proportions up to about 2% based on the total

  solids and about 4% based on the compound

  total detergent sition However, it should be noted that the nonionic organic surfactant of soap spaghetti provides at least a major part of the function of suspension of soiling and of anti-deposition, its effectiveness in this regard being greatly increased speak

  soap, as previously explained.

  Loads can also be incorporated

  in addition to the aforementioned ingredients, for example sul-

  sodium fate, sodium chloride, and the like La

  amount can reach about 40% of the total composition

tale -

  The detergent composition is prepared by conventional methods such as spray drying

  of a grinding mixture comprising a surfactant, an ad-

  said, charge, etc., with volatile ingredients such

  that an otherwise affected fragrance or ingredients

  by spray drying, for example a

  peroxygen bleaching agent such as sodium perborate

  dium Ingredients of this type are preferably mixed after the fact As previously mentioned, the soap spaghetti (possibly used) and the cationic softening mixture-nonionic compound are simply dry mixed with the dried detergent in particles by simple mixing.

  mechanical which is better suited to obtain a homo-

  gene As previously described, some or all

  soap spaghetti can alternatively be added to the mixture.

  An aqueous grinding mixture An example of the procedure is as follows: water, followed in sequence, by anionic component, sodium silicate, optional ingredients optionally used such as Satintone N is added to a grinder 2 and a filler such as sodium sulphate and the additive salt The grinding mixture is heated to approximately 60 ° C. before addition of the additive, for example sodium tripolyphosphate, and the solids content

  of the ground mixture before spray drying is about

  about 55-65% Spray drying can be carried out conventionally by pumping the hot mixture from the grinder into an atomization tower where the mixture passes through a spray nozzle to reach a hot evaporating atmosphere The bleaching agent and other materials remaining to be added are incorporated into the mass of cooled detergent and dried by any suitable means, for example by

simple mechanical mixing.

  In use, a sufficient amount of detergent composition is added to the washing cycle to obtain a concentration of cationic softener in the washing medium of approximately 1.5 to 8.0 g / 3500 g of laundry, within a range

  ranging from 21 C to boiling (i.e. about 100 C).

  In this respect, we realize that by washing "cold", we mean a washing temperature reaching 21 C, "hot"

  being between plus 21 C and boiling.

  Certain types of aliphatic ammonium compounds

  quaternary nium although relatively ineffective for a-

  softness are nevertheless quite effective as antistatic agents in the compositions of the invention

  and, in particular, the fact that they are physically compared

  tibles with the anionic surfactant in li-

  In general, these materials include the compounds

  ethoxylates and / or propoxylates of quaternary ammonium of

following mule:

CH +

R 7 5 R X

R 9

2539427 d

  in which R 7 and R 8 represent an ethoxy or pro-

  poxy, m and N are integers from 1 to 50 and may be the same or different and R 9 represents an alkyl group of 14 to 24 carbon atoms Compounds of this type include (a) methylbis- (2- hydroxyethyl) co-ammonium, a liquid containing 75% of active material in an isopropanol / water solvent and commercially available under the designation Ethoquad c / 12, Armak and Variquat 638 (registered trademarks), Sherex Chemical Co; (b) Ethoquad c / 25, as in (a) but having 15 moles of ethylene oxide (nm + N) and available at 95% of active material; (c) methylbis- (2-hydroxyethyl) octadecylammonium chloride, a liquid,

  % of active ingredient in isopropanol / water solvent

  commercially available under the designation Ethoquad 18/12, Armak and (d) as (c) but having 15 moles of oxide

  ethylene (m + n) a liquid with 95% of ac material

  tive and commercially available under the designation Ethoquad 18/15, Armak These materials can be used in proportions up to about 10% by weight of the

total composition.

  The following examples illustrate the invention without limiting it All parts and all percentages

are expressed by weight.

Example 1.

  A) 100 g of Arosurf TA powder (dimethyldistearyl ammonium chloride) is heated to 90 ° C. and one obtains

  thus a fluid melt We add to this melt

  due 10 g of liquid nonionic Neodol 23-6 5 (linear alcohol

  re in C 12 _ 13 condensed with 6.5 moles of ethylene oxide) The mixture is well stirred and then cooled to room temperature A white solid is obtained Then the solid is ground into a powder (passing entirely through a 2.38 mm mesh screen, less than 10% passing through the 0.149 mm mesh screen) The product looks like powder

starting Arosurf.

  B) We repeat Part A with the difference that

  uses only 5 g of non-ionic component.

Example 2.

  Each of the products of Example 1 and the cationic powder component are tested separately

  alone (the same as that used in Example 1 to obtain

  hold the co-molten product), of a particle size identical to that of the product of Example 1, to determine the uniformity of dispersion in water by the procedure

following.

  500 ml of water (hardness 150 ppm) at 21 ° C., 0.15 g of a detergent (13.4) are introduced into a "Tergotometer" apparatus fitted, as usual, with a reciprocating agitator. % alkylbenzene sulfonate; 24% sodium tripolyphosphate; 30% sodium sulfate; 4.5% sodium carbonate; 6.3% solids such as water-soluble silicate; 7% humidity; 4% soap; minor amounts of brightening agent, methocel and perfume) which also contains 4.5% of the particles of Example 1 The agitator is started for 5 minutes at 100 rpm and then vacuum filter the aqueous composition through a new smooth blue cotton-crossover fabric In the case of the liquors containing the detergent of Example 1, no visible signs are observed (that is to say, no white spots ) residue When the procedure is repeated using identical conditions with the same composition, with the difference that in place of the 4.5% of the products of

  Example 1, 4.5% cationic compound is used for

  dre alone, we notice a very visible mark of white spots on the cross cotton fabric This highlights

  the remarkable advantages of the products of Example 1.

Example 3.

  When the compositions described in Example 2 are used to wash white towels soiled in a washing machine and then dried in an automatic dryer, the clothes, in each case, are sufficiently flexible although those washed with the detergent containing the softener combination of example 1 are slightly more flexible In addition, the towels washed with the detergent containing the cationic powder compound

  alone (i.e. not combined with the nonionic agent) pre-

  feel some degree of visible but light stain formation (i.e., grease stains) apparently due to the cationic material, while others do not

not this drawback.

Example 4.

  Examples 1 A and 1 B and 3 are repeated at different times.

  the following nonionic compounds are used

in place of Neodol 23-6 5.

  a) Neodol 25-7 (linear C 12 _ 15 alkyl alcohol + 7 moles of ethylene oxide). b) Igepal C 0-630

  (nonylphenol + 10 moles of ethylene oxide).

  c) Neodol 45-13 (linear C 14 _ 15 alkyl alcohol + 13 moles of ethylene oxide).

Example 5.

  A very powerful detergent, spray-dried, having the following composition is prepared: Component% by weight Linear tridecylbenzenesulfonate (LTBS) 15 Sodium tripolyphosphate (Na TPP) 33 Silicate 7 Brightening agent (Stilbene and Tinopal 5 BM) 0.48 Sodium sulfate and water 44.52.00 To 90 g of the above composition, 4 g of the cationic-nonionic powder of example 1, part B, are added.

Excellent results are obtained.

Example 6.

  Example 3 is repeated with the difference that the detergent also contains soap spaghetti (4.5%

in the detergent).

Example 7.

  Example 6 is repeated, with the difference that the

  soap spaghetti contains 20% by weight of Neodol 25-7.

  In examples 6 and 7, the soap spaghetti consists of an 85/15 mixture of tallow soap / soap

coconut.

Example 8.

  Example 3 is repeated, but using a

  detergent composition having the following rough analysis.

  Component% by weight Linear dodecylbenzenesulfonate 23 Na 2 CO 3 20 Silicate 15 Borax 3 Non-ionic surfactant 1 Soap 2 Carboxymethylcellulose 1 Brightening agent (Stilbene and Tinopal 5 BM) 0.48 Satintone 1 Na 2 SO 4 and water qs 100 to 95 g of the above composition, g of the product of Example 1 B is added -

Example 9.

  We repeat example 8, with the difference that we use

  read 5 g of non-ionic spaghetti soap (similar to

Example 7).

Example 10.

  Example 6 is repeated, with the difference that the spaghetti soap used also contains 4% by weight

of carboxymethyl cellulose.

2539427 d

Example 11.

  The detergent composition is prepared very then-

next health.

  Component% in poi <Linear alkylbenzene-sulfonate 9 Alcohol-ethersulfate 8 Non-ionic surfactant 2 Sodium tripolyphosphate 24 Zeolite A 17 Na 2504, brightening agent, water qs 100 5.0 g of the product are added to this composition cationic of example l B.

Example 12.

  Example 11 is repeated with the difference adding the soap / nonionic surfactant spaghetti

  ple 6 in a proportion of 4% in the detergent.

Example 13.

that we

of the example

  A powder detergent composition is prepared

  unscented having the following formulation.

  Component% by weight Tridecylbenzene-sulfonate linear 14.8 Sodium tripolyphosphate 26.5 Silicate 6.9 Brightening agent (Stilbene and Tinopal 5 BM) 0.47 Sodium carbonate 4.9 Carboxymethyl-cellulose 0.25 Methocel 0, 6

Sodium sulfate, moisture q s.

  The following ingredients are added to 90.6 parts by weight of the unscented powder detergent above: Cationic-nonionic mixture of Example 1 B 4.0 parts Spaghetti soap (90% 85/15 tallow / coconut ;% of Neodol 25-7 (Shell Chemical Co), length of spaghetti = 15 mm, diameter = 0.5 mm 4.0 parts Borax pentahydrate 0.7 parts ds

2539427 J

  Non-ionic surfactant (Neodol 25-7) 0.5 part Perfume 0.2 part The following examples illustrate the production and use of the cationic-non-ionic combination in tablet form.

Example 14.

  500 kg of dimethyldistear chloride are heated

  ryl-ammonium containing about 4% of water at 90 ° C. to obtain a melt Add to this hot melt 25

  kg of Neodol 23-6 5 This mass is then sprayed

  naked down from the top of a tower of about 24 meters and about 5 meters in diameter At the same time, cooling air is raised to about 100 C

  (i.e. against the current compared to the spraying -

  downward) at a speed of 8490 m 3 per minute On

  collects the frozen product at the bottom of the tower

  product cules are white, fluid, generally

  spherical and solid They have a porous surface (marked appearance) The apparent density of a pellet

is approximately 0.37 g / cm 3.

Example 15.

  4.5 g of the tablets are added to 95.5 g of the detergent of Example 2 (without the particles of Example 1)

Example 14.

Example 16.

  Each of Examples 5 to 13 is repeated at the different

  rence that the nonionic cationic mixture used in

  these examples are replaced by the pellets of example 14.

Example 17.

  Each of the preceding examples is repeated at

  difference than the nonionic compound in the cationic mixture-

  non-ionic is used in proportions of 2%, 7%, 12%,

%, 20%.

Example 18.

  Each of the preceding examples is repeated again.

  teeth with the difference that the cationic softener of the met

  cationic-nonionic mixture is replaced by the following compounds: (a) dimethyl-di- (tallow) -ammonium methosulfate, (b) dimethyl chloride, di (hydrogenated tallow) ammonium,

  (c) methyl-1-tallow-amido-ethyl-2-tallow methosulfate-

imidazolinium,

  (d) m 1-methyl-1-oleylamidoethyl-2-oleyl beta sulfate

imidazolinium.

Example 19.

  In each of the preceding examples, when the particles of cationic-nonionic mixture are used

  when mixed with the detergent, the amount of catio-

  non-ionic nique varies to give 2%, 7% and 10% on the

  based on the weight of the detergent and softener particles.

  Among the nonionic substances which are useful in the cationic-nonionic combination, it is

  obvious that there is a wide range of melting points.

  Thus, Neodol 23-6 5 is a liquid nonionic similarly

  than Igepal CO-630 (nonylphenol plus 10 moles of oxide of

  thylene), while Neodol 25-7 is a fairly pasty solid and Neodol 25-12 is a white soft solid Has a higher content of ethylene oxide (i.e. more moles of oxide 'ethylene), the product becomes more solid

  and fairly waxy to the touch and appearance.

  In particular, when it is desired to use higher proportions (that is to say more than about 5 to%) of nonionic compound in the cationic melt, it is often advantageous to use a mixture of a nonionic compound. liquid ionic and a solid nonionic compound In addition to the solid nonionic ethoxylated compounds, it is also possible to use other solid or pasty compounds such as glycerides which are fatty mono or diesters of glycerol. in this regard glycerol monostearate, glycerol mono-oleate and

* 2539427,

glycerol palmitate.

Example 20.

  Example 1 A is repeated with the difference that half of the nonionic Neodol is replaced by glycerol monostearate. In the test procedure of Example 2, this product rivals the material of Example l A.

Example 21.

  Example 3 is repeated using the product of

  example 20 instead of the cationic materials of example

  ple 3 Excellent results are obtained.

Example 22.

  Example 7 is repeated with the difference that the de-

  tergent contains the combination of tertiary softener from example 20 instead of the binary combinations from example

  1 The results are as good as those of Examples 3 and 7.

Example 23.

  Example 22 is repeated with the difference that the non-ionic used is Neodol 45-11 (a linear alcohol

  C 14 _ 15 plus 11 moles of ethylene oxide).

Example 24.

  We repeat Example 6 with the difference that the

  soap spaghetti is replaced by an equal weight of cris-

  Carbowax level (molecular weight 3000-8000).

Example 25.

  Example 24 is repeated with the difference that the amount of Carbowax is modified as follows (% in the detergent): (a) 0.5 (b) 1.0 (c) 2.0 (d) 4.0

Example 26.

  We repeat each of examples 6, 7, 9, 10, 12, 13, 16, 17, 18, 19, 21, 22 and 23 with the difference that the soap spaghetti is replaced by the Carbowax used

2539427 J

  in examples 24 and 25 in the quantities indicated (% on

base of detergent weight).

(a) 0.2 (b) 0.4 (c) 0.8 (d) 1.0

(e) 2.0 -

(f) 3.0

(g) 5.0.

Example 27.

  Examples 24, 25 and 26 are repeated, using the following ingredients in place of Carbowax: (A) Pluronic crystals F-108, (B) Spaghetti of soap having a high solubility in water containing (a) 10 % sodium xylene sulfonate;

  (b) 20% sodium xylene sulfonate; (c) 40% xylene-

sodium sulfonate.

  The Carbowax product of Examples 24 to 26 is a polyethylene glycol The Pluronic F-108 product of Example

  27 is a block polymer of polyoxypropylene-polyoxyethyl-

  lene containing 20% of polyoxypropylene groups as hydro-

  phobic and 80% of polyoxyethylene groups The hydrophobic of

  base has a molecular weight of 3250.

  The Pluronic F-108 product is also represented

  tative of water-soluble nonionic compounds that are useful

  in cationic-nonionic melts of the pre-

  sente invention Pluronic are of particular interest

  liquids containing up to about 50% polyoxy-

  ethylene and a molecular weight of the hydrophobic base of the polyoxypropylene moiety of about 950 to 4000 When combinations of, for example, Neodol 23-6 5 and Pluronic are used, it may be preferable to use pasty or solid Pluronic These generally contain from 25% to 80% of polyoxyethylene groups. Examples of liquid Pluronic products are Pluronic L-61, Pluronic L-64, 2539427 i Pluronic L-72 and Pluronic 101; among the pasty Pluronic, the applicant may cite the Pluronic P-85 and the Pluronic P-105 among others; among solid products we can

  cite the Pluronic F-87 and the Pluronic F-27.

Example 28.

  As an example of the advantages of the present in-

  vention, consisting in preventing the formation of stains, several different dirty white materials are washed at 21 C.

  and 49 C using the detergent containing the compound ca-

  ionic alone, (A) on the one hand and the tablet of cationic-nonionic compound of Example 14 on the other hand (B) The

  detergent is that described in Example 2.

  All the white materials are evenly soiled and the reflectance values of the washed materials are measured. The following reflectance values (Rd) are obtained:

21 OC 49 C

(A) (B) (A) (B)

  Spun dacron 77.7 79.0 64.7 66.5 Dacron / cotton (65/35) 81.4 81.5 73.9 76.1 Cotton 87.8 87.8 87.3 87.3 Nylon 84, 1 85.2 84.1 84.5 The above clearly demonstrates that even after a single wash, there is a marked improvement on Dacron spun at two washing temperatures, on Dacron / cotton at 49 ° C and on Nylon at 21 C A difference

  of 0.5 unit Rd is significant in the sense that this dif-

  ference is detectable visually 2,539,427 l

Claims (16)

  1 Particular detergent softening composition   particle glass capable of imparting better pro-   flexibility, detergency, antistatic and anti   formation of stains on fabrics treated with this composition during a laundering operation, characterized in that it contains, by weight, approximately 5 to 40% of an organic surfactant without water-soluble soap, approximately 60% of a neutral to alkaline water-soluble additive salt,   about 2 to 20% of softening cationic amine mixture-   non-ionic compound, and about 0-20% acid soap   fat soluble or dispersible in water or a mixture thereof   itself with a nonionic organic surfactant, the non   ionic constituting from about 2 to about 50% by weight of the   said soap mixture, the cationic agent-non-agent mixture   ionic being dispersed substantially homogeneously in   said composition in the form of discrete particles.   2 Composition according to claim 1, charac-   terized in that said cationic agent is a halide   of quaternary ammonium and the nonionic compound is an etho- water-soluble xylate.   3 Composition according to claim 2, charac-   realized in that the nonionic agent constitutes approximately 2 to 20% of said mixture, and the mixture constitutes approximately 2 about 15% of said detergent.   4 Composition according to claim 3, charac-   terized in that said cationic compound is a short chain dialkyl halide, long chain dialkyl halide   quaternary ammonium, said non-ionic compound is an etho-   xylate of a C 8 to C 30 aliphatic alcohol, a thiol amide or an alkylated amine or phenol, or a thiophenol containing from about 3 to about 100 moles of ethylene oxide; said nonionic agent constituting from about 2% to about 15%   by weight of said cationic-nonionic mixture, and said   diaper constituting from approximately 2 to approximately 10% of said detergent.   2539427 l Composition according to claim 4, characterized in that said soap-free detergent contains an alkylbenzene sulfonate, said additive comprises a phosphate, said cationic agent is a di (C 1 -C 4 alkyl) halide, di (C 14 -C 18 alkyl) ammonium, said nonionic   is a linear C 8 to C 18 aliphatic alcohol ethoxylated   taking from about 3 to about 50 moles of ethylene oxide and said nonionic constitutes from about 3 to about 10% by   weight of said cationic-nonionic mixture.   6 Composition according to claim 5, charac-   terized in that the cationic-nonionic mixture is under form of pellets.   7 Composition according to claim 5, charac-   terized in that said cationic-nonionic mixture is the finely ground product of a melt of the component   cationic and non-ionic component.   8 Composition according to claim 5, charac-   terized in that said pellets are central particles   generally spherical solids with porous surfaces.   9 Composition according to claim 3, charac-   terized in that the surfactant is an alkylbenzene-sulfo-   linear C 8 to C 18 nate, catalytic amine softener   is chosen from the group comprising the salts of (di-   C 1 -C 4 alkyl), (C 14 C 18 dialkyl) ammonium quater-   nary, the imidazolinium salts and their mixtures and the nonionic of the cationic-nonionic mixture is a linear C 8 C 18 aliphatic alkanol containing from about 6 to   about 20 moles of ethylene oxide.   Composition according to claim 9, charac-   terized in that the nonionic is a liquid nonionic   and constitutes approximately 2 to 10% by weight of the cationic mixture que-non-ionique.   11 Composition according to claim 10, charac-   terized in cc which it contains as adjuvant mono or   diester of glycol or glycerol of a C 8 to C 18 fatty acid.   12 Composition according to claim 11, charac-   terized in that the adjuvant is glycerol monostearate.   13 Composition according to claim 12, charac-   terized in that the amount of glycerol monostearate is from about 1 to about 20% based on the weight of the cationic-nonionic mixture and constitutes a component of this mixture.   14 Process for the preparation of the composition   lon claim 1, characterized in that it consists in spray-drying the organic surfactant without soap and the additive salt and in adding the rest of the ingredients to the spray dried material.   Softening composition cooled by atomi-   sation characterized in that it contains an intimate mixture of a softener of the cationic amine type and from 2 to 20% based on the weight of said mixture of a surfactant-ethoxylate non-ionic water-soluble.   16, Composition according to claim 15, charac-   terized in that the ethoxylate is an aliphatic alcohol li-   in C 8 to C 18 and the amount of ethylene oxide combined   is about 5 to about 100 moles.   17 Composition according to claim 16, charac-   terized in that the amount of non-ionic is between about 2 and about 10%.   18 Composition according to claim 17, charac-   terized in that it contains about 2 to 20% of a mono-   or glycerol or glycerol diester of a C 8 to C 18 fatty acid.   19 Composition according to claim 18, charac-   terized in that it contains about 2 to about 10% of glycerol monostearate.   Method for cleaning and softening linen, characterized in that it consists in washing said linen   in an aqueous medium containing the composition according to the vendication 1.