JPH07509522A - How to use modified polyester to remove oil-based stains on fabrics - Google Patents

Abstract

The present invention relates to the use of selected modified polyesters known for their soil-release properties as cleaning agents for cotton-containing fabrics, thus being able to provide a cleaning effect on such fabrics after only one laundering cycle, as compared to several cycles when functioning in the soil-release agent mode. The present invention also encompasses detergent compositions containing said modified polyesters and a cellulase enzyme, or a co-dispersing agent and/or a soil-antiredeposition agent.

Description

[Detailed description of the invention] How to use modified polyester to remove oil-based stains on fabrics Technical field The present invention uses modified polymers known for their dirt removal properties with nonionic surface activity. A modified cleaning agent used in conjunction with a cleaning agent to remove oil-based stains on fabrics. Concerning the use of polymers.

Background of the invention Products used in laundry operations contain numerous ingredients that provide certain basic benefits. It is rare. For example, cleaning products used in the cleaning industry collect various types of dirt during cleaning. Detergent/surfactant systems have been formulated to remove phthalate from clothing. Cree Some of these products used in the cleaning industry have properties such as softening and antistatic properties that can be improved through cleaning. It also contains ingredients that soften and condition the fabric.

Detergents used in the cleaning industry have standard cleaning properties, flexibility and antistatic properties. In addition to this, other desirable properties can be imparted to the woven fabric. Part one One is the ability to impart stain releasability to polyester fiber woven fabrics. polyester Woven fabrics are hydrophobic, so they are not easy to clean and are susceptible to oil stains and stains. This is particularly difficult when Oil-based stains or stains preferentially wet woven fabrics. oil-based dirt or stains are difficult to remove with water-based cleaning methods. be.

Certain polyester compounds can be incorporated into detergent compositions used in the cleaning industry. It has already been found that it exhibits stain removal properties. Cleaning in progress These stain-releasable polyesters are adsorbed onto the surface of woven fabrics soaked in cleaning solutions. It will be done. The adsorbed polyester then forms a hydrophilic film, which remains on the fabric even after it has been removed from the cleaning solution and dried.

This film is subsequently washed with a stain-removing polyester-containing detergent composition on the woven fabric. Then it will play.

Such polyesters are described, for example, in U.S. Pat. No. 4,711,730.

Research to improve stain-removable polyester is continuing9, for example, EPA No. Publication No. 272033 contains a description of such an improved polyester. recently Well then.

In EPA No. 311372, polyester whose terminals are capped with sulfaroyl groups There is a disclosure of an improved soil release agent comprising Stell.

Certain modified polyesters described in EPA No. 311342 are polyesters. It not only functions as a stain remover for woven fabrics, but also removes stains from cotton blend woven fabrics. During the main cycles of the cleaning process, such soils may be dispersed. (See EP 92.202°383.3).

- Removal of oil-based stains by cleaning is a long-standing concern. Currently on the market This detergent composition can efficiently remove oil stains from woven fabrics, especially polyester woven fabrics. It is difficult to do so.

This time, surprisingly, the modified polyester described in EPA No. 133.342 was When used in conjunction with certain nonionic surfactants with a low degree of oxygenation, it removes oil-based stains from woven fabrics. It has been found to be surprisingly effective in removing

The detergent composition of this invention contains dimethyl terephthalate, dimethyl sulfoisophthalate, Random copolymerization from salt, ethylene glycol and 1,2-propanediol A modified polyester that is a polymer in which most of the end groups are sulfobenzoate. The remaining part is ethylene glycol and/or propanediol monoester. a modified polyester secondary to alcohol, and 2 to 5 moles per molecule of alcohol. C-grade alcohol ethoxylate with ethylene oxide (E, O,) added It consists of a nonionic surfactant. The most preferred nonionic surfactant is CI2- 15-alcohol ethoxylate (E, 0.3 mole addition) nonionic surfactant It is. This is present in a ratio of 1:0.3 to 1:2.0 based on the detergent composition. It also exhibits an unexpected thickening effect. By utilizing this phenomenon, the specific nonion Surfactants can be made into granular detergents.

Further, in the present invention, the flamed modified polyester can be used at the specific nonionic interface. It has been found to exhibit a thickening effect on active agents.

The modified polyester of this invention includes dimethyl terephthalate, dimethyl sulfoiso Obtained from phthalate, ethylene glycol and 1,2-propanediol It is a random copolymer, and most of its terminal groups consist of sulfobenzoate. The remaining end groups are monoesters of ethylene glycol and/or propanediol. consists of secondary elements. The target polymer has “most” sulfobenzoate at both ends. It is a polymer capped with a group of Most of the polymers will be end-capped with sulfobenzoate groups. death However, some copolymers are not completely capped, and in this case the polymer end The end groups are monoesters of ethylene glycol and/or propane 1,2-diol. in this sense, the terminus is "secondarily" ethylene glycol and/or or a monoester of propane 1,2-diol.

Certain polyesters of the present invention contain about 46% dimethyl terephthalic acid, about 1% dimethyl terephthalic acid, by weight. 6% propanediol, about 10% ethylene glycol, about 13% dimethyl Contains sulfobenzoic acid, and approximately 15% sulfoisophthalic acid, and has a molecular weight of is approximately 3.000. This polyester and its manufacturing method comply with EPA No. 31134. More details in issue 2.

Furthermore, together with the modified polyesters of this invention, cellulase enzymes and/or Combined with species co-dispersants and/or certain nonionic surfactants, excellent It was found that a cleaning effect can be obtained.

Nonionic surfactant The ionic surfactant of this invention contains 2 to 2 ethylene oxides per molecule of alcohol. It is a C8 to C18 alcohol ethoxylate to which 5 moles are added. Like The new ethoxylate is C12-15' alcohol ethoxylate (E, 0.3 molar adduct).

The modified polyester content in the detergent composition of this invention is relative to the nonionic surfactant. The ratio is 1:0.3 to 1:20, preferably 1:6 to 1:20.

detergent composition The detergent compositions described herein may be in liquid or granular form and may be applied directly to the machine casing rather than indirectly. Preferably, the material is fed directly into the drum via a drum. This purpose is for bags or The packaged detergent composition is agitated, heated, or immersed in the wash water in a drum. by ensuring that it is released from the container at the beginning of the cleaning cycle in response to can be easily achieved. Such a container is placed in a drum together with the fabric to be cleaned. You may. Alternatively, drum The washing machine itself may be adapted so that the detergent composition can be added directly into it.

If the composition is in liquid form, a rigid container such as that described in EPA No. 151549 may be used. Wear. Preferably, it is in the form of granules, in which case bags or cloth bags, etc. flexible containers are used. Retains contents in a fibrous bag coated with waterproof material (see EPA No. 0018678). Alternative Law and Siteha, EPA No. 001 No. 1500, No. 0011501, No. 0011502 and No. 0011 End seals or fasteners tearable in an aqueous medium, such as those disclosed in US Pat. The container may be made of a water-insoluble synthetic polymeric material provided with a material. Can be opened with water Simple fasteners are made from water-impermeable polymeric films such as polyethylene or polypropylene. Water applied along one edge of a pouch consisting of a film and sealing the ends of the brackets. Consists of soluble adhesive.

Among the variety of bags or containers, laminated sheet products can also be adopted. here soaks and/or coats the central flexible layer with a detergent composition and then applies one or two layers. A woven fabric-like appearance is imparted to the above outer layer. Seal each layer to each other during use impregnated materials or coatings that remain in contact or separate from each other upon contact with water. Facilitates the release of chemicals.

Another form of laminate is embossed to form a series of pouch-like containers. or a deformed single layer, into which a certain amount of the detergent composition is placed. and sealing thereon a second layer that overlaps the first layer in the area between the pouch-like containers. It has a structure in which two layers are in contact with each other in a region. Detergent composition is particulate, paste It can be in solid or molten form, and as a laminate layer, the content remains until it is added to water. Select materials that do not allow material to leak out of the container.

On contact with water these layers can separate or remain in contact with each other, but only One thing that is needed is a structure that allows the contents of the pouch-like container to be quickly released and become a solution. It is in.

The number of pouch-like containers per unit area of the base layer is arbitrary, but usually 5 per square meter. 00 and 25000.

Materials for the flexible laminate layer used in this invention include sponge, paper, woven fabric, and Examples include nonwoven fabrics.

Examples of suitable means for carrying out the cleaning method of the invention include liquid permeable Those using reusable lightweight dispensing devices with impermeable walls for solid compositions law is included. This type of device is EPA No. 0343069 and EPA No. There is a disclosure in Publication No. 44070.

The latter application describes a support ring extending from a support ring defining an orifice. A device is disclosed consisting of a flexible sheet in the form of a bag, the orifice of which is Enables the bag to be filled with enough detergent product for one wash cycle during the cycle It is considered. Some of the cleaning medium flows into the bag via the orifice and The product is dissolved and the solution is then passed upward through the orifice and into the cleaning medium. child The support ring is equipped with a shielding device to prevent regression of wet, undissolved product. this device The array typically extends radially from the central boss of the spoked wheel shape. or from a similar structure in which the walls are helical. Become.

The detergent composition here includes a surfactant.

There are many different types of surfactants used in detergent compositions. anion, nonion , amphoteric, zwitterionic surfactants, and the compounds that make up these surfactants. Regarding products, see US Pat. No. 3,664,961 (Norris) (19 The disclosure was made on March 23, 1972).

Anionic surfactant mixtures are particularly preferred for the purposes of the invention, especially sulfone surfactants. and sulfate in a ratio of 5.1 to 1:2 by weight, more preferably Or a composition of 3:1 to 1.1. Examples of preferred sulfonates include alkaline Alkylbenzene sulfonates whose kill group has 9 to 15 carbon atoms, especially 11 to 13 carbon atoms , and from C12 to C18 fatty chains, preferably from C16 to 01B fatty chains. α-sulfonated methyl fatty acids of conventional fatty acids are included. In each case, click On is an alkali metal, preferably sodium. Preferred sulfate interface Examples of activators include alkyl sulfates in which the alkyl group has 12 to 18 carbon atoms. an ethyl group containing 10 to 20 carbon atoms, preferably 10 to 16 carbon atoms in the alkyl group; It is used optionally mixed with cisulfate (E, 0.1 to 6 molar adduct).

Examples of suitable alkyl sulfates for use in this invention include tallow alkyl sulfates. ate, coconut oil alkyl sulfate, and C alkyl sulfate +4-15 Fete is included. A good example of ethoxy sulfate is the so-called AE3S [ Examples include C-alkyl ethoxylated sulfate (E, 0.3 mol adduct).

Each cation is an alkali metal, preferably sodium.

Particularly preferred nonionic surfactants for use in the present invention have an average HLB of 5 to 1. 7, preferably 6 to 14, more preferably 7 to 12 surfactants. It is an ethylene oxide (E, O,) condensate with a hydrophobic site. This hydrophobic site That is, the lipophilic moiety is an aliphatic or aromatic moiety that is fused with this lipophilic group. By adjusting the length of the polyoxyethylene group, the difference between hydrophilic and lipophilic elements can be adjusted. The balance allows the desired degree of water-soluble compound to be formed.

In addition to the specific nonionic surfactants described herein, C-class alcohol salts may also be present in the composition. toxylates (E, 6 to 8 moles added at 0°), especially C-alcohol ethoxylates Additionally contains a nonionic surfactant such as sylate (addition of 6 to 8 moles of E, O, etc.). may be included.

Other good examples of nonionic surfactants include the following general formula (%) [In the formula, Z is a moiety derived from glucose, and R is a lipophilic atom having 12 to 18 carbon atoms. alkyl group, t is a number from 0 to 10, n is 2 or 3, and x is 1.3 to 10. 4] is included, and this compound Contains less than 10% unreacted fatty alcohol and less than 50% short chain alkyl poly Contains glucosides.

Examples of preferred additional nonionic surfactants include the following [wherein R is C hydrocarbyl] 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof. , R is C hydrocarbyl, Z has at least 3 hydroxyls directly attached to the chain. polyhydroxyhydrocarbyl containing a linear hydrocarpyl chain, or its derivatives [indicates a rukoxylated derivative]. R1 is methyl, R2 is coconut oil alkyl or its Straight chain Cll-15 alkyl or alkenyl chains such as mixtures are preferred, and z is a group In the reductive amination reaction of cose, fructose, maltose, lactose, etc. Derived from reducing sugars.

Other surfactants include semipolar surfactants such as amino oxides. good Preferred amine oxides include C8-20' and more preferably C-N-alkyl or or 4 per day alkenylamine oxide, and propylene-1,3-diamine dioxide ( However, the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups. ) is included.

Other surfactants include amphoteric surfactants such as polyamine compounds. Catio C8 surfactants can also be used in the present invention, and quaternary ammonium surfactants include C8 -16, preferably CN-alkyl or alkenylane Q-14 monium surfactant (however, the remaining N positions are methyl, hydroxyethyl or hydrochloride) (substituted with oxypropyl group) are preferred.

The use of mixed surfactants, especially anionic-nonionic and anionic-nonionic-carbon Preference is given to using thionic mixtures. Among them, British Patent No. 2040987 and European Patent No. The use of mixed surfactants as disclosed in State Patent Publication No. 0087914 is preferred.

The detergent composition contains 1 to 70% surfactant by weight; The usual content of the agent is 1 to 30%, more preferably 10 to 25%.

Typical builder content is from 5 to 80% in detergent compositions. used in this invention The composition contains no or substantially no phosphate-containing builders. (The term ``free of detergent'' specifies that it is less than 1% in the total detergent builder system) , the builder system in parentheses may be a water-soluble builder, a water-insoluble builder, or consisting of a mixture of

Water-insoluble builders are typically inorganic hydrated aluminosilicate materials, more specifically consists of hydrated synthetic zeolites, such as hydrated zeolites A1X, B or R3. Composed of inorganic ion exchange material.

The preferred aluminosilicate ion exchange material has the following unit cell general formula: %formula% [wherein M is a calcium exchange cation, Z and Y are at least 6, and the model of Z versus Y is X is at least 5, preferably 7.5 to 27 6, more preferably 10 to 264].

The aluminosilicate material is in hydrated form and preferably contains 10 to 28% More preferred are crystals containing 10 to 22% water of crystallization.

A further characteristic of the aluminosilicate ion exchange material is that the particle diameter is between 0.1 and 1. 10 micron meters, preferably 0.2 to 4 micron meters be.

The term "particle diameter" is defined using known analytical techniques, e.g. using scanning electron microscopy. refers to the diameter measured by Further characteristics of this aluminosilicate ion exchange material Calcium ion exchange with a hardness/g equivalent of at least 200 mg and generally 300mg　eq./g　~352mg It is in the range of eq, /g. Other properties are described in British Patent No. 1429143 It is characterized by its calcium ion exchange rate.

The aluminosilicate ion exchange material that can be used in the present invention is commercially available, and natural Although any material can be used, synthetic materials are preferable. aluminosilicate Methods for synthesizing ion exchange materials are discussed in U.S. Pat. No. 3,985,669. Ru. Crystalline synthetic aluminosilicate ion exchange materials are “zeolite A” and “zeo "Lite B", "Zeolite X", "Zeolite H3J" (all product names), and It is commercially available as both and a mixture thereof. Among them, “zeolite A” is preferable. It is a crystalline aluminosilicate ion exchange material commercially available as % [In the formula, X is 20 to 30, particularly 27.

"Zeo Light X” is also a formula% formula% The "zeolite H8" shown is also preferably used.

Examples of water-insoluble inorganic building blocks that can be suitably used include rSKS-64 (hexyl Included are layered silicates commercially available from Str. rS　K　S　-6 J is a crystalline layered silicate consisting of sodium silicate (Na2Si205) It is. The high Ca/Mg binding ability is mainly due to the cation exchange mechanism.

Solubility is further improved in hot water.

Water-soluble builders are carboxylate chelates consisting of monomers or oligomers. It can also be a curing agent.

- Suitable carboxylates with carboxy groups include lactic acid, glycolytic acid, acid, and their ether derivatives (Belgium Patent No. 831368 and 821.369 and 821,370). two Examples of polycarboxylates containing carboxy groups include succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartro acid, fumaric acid and West German Published Patent Application Nos. 2-446686 and 244668 Ether carboxylates described in Publication No. 7 and U.S. Pat. No. 3,935,257 and the sulfnyl carboxylate disclosed in Belgian Patent No. 840,623. is included. The polycarboxylate containing three carboxyl groups has , especially water-soluble citrate, aconitate, citraconate as well as e.g. Succinic acid derivatives such as carboxymethyloxysuccinate described in Japanese Patent No. 1379241 conductor, lactoxysuccinate, as disclosed in Dutch Patent Application No. 7205872; and 2-oxa-1,1,30 proppant as described in British Patent No. 1387447. Included are oxypolycarboxylates such as recarboxylate.

British patent no. Oxydisuccinate, 1,1,2,2-ethanetetracal described in No. 261829 boxylate, 1,1,3.3-propanetetracarboxylate and 1,1 , 2,3-tetracarboxylate. Sulfo substituent-containing polycarbo British Patent No. 1398421 and British Patent No. 1398422 are among the targets of xylate. and the sulfosuccinate derivatives disclosed in U.S. Pat. No. 3,936,448; Includes sulfonated pyrolyzed citrate described in National Patent No. 1082179, Polyacrylates containing sulfone substituents are described in British Patent No. 1439000. There is a list.

Among the alicyclic and heterocyclic polycarboxylates are cyclopentane-cis , cis, cis-tetracarboxylate, cyclopentadienide pentaka ruboxylate, 2.3.4-5-tetrahydrolane-cis, cis, cis -tetracarboxylate, 2. 5-tetrahydrofuran-cis-dicarbo Xylate,.

2.5.5-Tetrahydrofuran-tetracarboxylate, 1,2.3.4. 5.6-Hexanehexacarboxylate, and sorbitol, mannitol and and capoxymethyl derivatives of polyhydric alcohols such as xylitol. Yoshi Among the aromatic polycarboxylates are mellitic acid, pyromellitic acid, and Phthalic acid derivatives disclosed in Japanese Patent No. 1425343 are included.

Among the preferred polycarboxylates are those containing up to 3 carboxyl groups per mole. hydroxycarboxylates, especially citrate.

Among the preferred builders are water-insoluble aluminosilicates such as Zeolite A. Builder or layered silicate (SKS/6) and water-soluble carboxylate chelate Mixtures with toning agents are included.

Other builder materials forming part of the builder materials of this invention include alkaline Inorganic materials such as metal carbonates, bicarbonates, silicates, etc. are included.

Other preferred water-soluble organic salts include up to two carbon atoms, separated from each other by atoms. A homozygous acid derived from polycarboxylic acid consisting of at least two carboxyl groups or a copolymer acid.

Copolymers of this type are described in British Patent Application No. 1,596,756. such salts Examples include polyacrylates with a molecular weight of 2,000 to 5,000; Mention may be made of copolymers of 20,000 to 40,000 in particular with maleic anhydride.

In one preferred embodiment of the invention, the detergent composition contains 0.025% to Contains about 10% of the above cellulase enzyme.

In an example of another preferred embodiment of the invention, the detergent composition or detergent additive Contains dirt redeposition prevention agent or dirt suspending agent along with modified polyester. .

Methyl cellulose and carboxymethylene are used as soil redeposition inhibitors and soil suspending agents. Cellulose derivatives such as cellulose and hydroxyethyl cellulose, and copolymers of polycarboxylic acid and its salts and polyamino acid compounds. Can be mentioned. The target of this type of polymer is the polyacrylic acid listed earlier as a builder. Includes rylates and maleic anhydride/acrylic acid copolymers; Copolymers of leic acid and ethylene, methylvinyl nitrate, or methacrylic acid and the maleic anhydride accounts for at least 20 mol% of the copolymer. . Polyamino acids such as derivatives derived from aspartic acid are described, for example, in British Patent Application No. 922. The disclosure is in No. 6942.2.

The detergent composition of this invention is preferably granular, more preferably "compact". )” form, i.e. of higher density than that of known detergent compositions. The new density range is 550 to 950 g/L, preferably 650 to 850 g/L ( 20°C).

The term “compact” in terms of morphology is appropriately influenced by the content of inorganic filler salts. Inorganic filler salts are present in significant amounts in all compositions, typically in known detergent formulations. It is contained in the powder detergent composition in an amount of 17 to 35% by weight, and is a known component in powder detergent compositions. Configure.

In the most preferred compositions, the filler salt content exceeds 15% by weight of the total composition. preferably not more than 10%, more preferably not more than 5%. It has a high concentration.

Are inorganic filler salts sulfates and chlorides of alkali metals and alkaline earth metals? Washed.

Sodium sulfate is the preferred filler salt.

The detergent composition of the present invention optionally contains components that normally constitute a part of the detergent composition. can do. Enzymes, optical brighteners, bleaching agents, bleach activators, bubble suppressants, coagulation Inhibitors, dyes, and pigments are examples of optional ingredients, used in concentrations as required. .

Enzymes such as protease, cellulase, lipase, or amylase are are particularly useful in detergent compositions, with cellulases being preferred.

Cellulases that can be used with the modified polyesters described herein have an optimum pH of 5 and above. It is a bacterial or fungal serylase between 9.5 and 9.5.

Suitable cellulases are described in British Patent Application Nos. 2075028 and 209. No. 5275 and DE-O3-2447832.

An example of such a cellulase is Lmicola in+olcns (Humic ola grisea var, thermoidex) strains, especially Humic Cellulase produced by ola DSM 1800 strain and genus Cellulase 212-producing molds belonging to Aeromonas and mar ine mullosc (DolabellxAuricula 5olan This is cellulase extracted from the hepatopancreas of de+).

The cellulase is added to the composition in the form of dust-free granules, such as "I" Ume. It may be in the s' or "l1llills" form, or as an example of cellulase. cellulase concentrate suspended in a nonionic surfactant or dissolved in an aqueous medium; It may also be supplied. The properties of cellulases suitable for use are determined by the C14CMC-method (E Immobilized radiolabeled carboxymethyl according to PA No. 350098) Cellulose can be removed by at least 10%.

In this test, 25 x 10'% by weight of cellulase protein was dissolved in the wash test solution. are doing.

A more preferred cellulase is described in International Patent Application No. WO91/17243. belongs to. For example, cellulase preparations useful in this invention are homogeneous It consists essentially of the component glucanase, which contains 1 (umico!a 1n Made from high purity 43kD cellulase derived from solen+ DSIJ 1800 antibodies are immunoreactive or directed against the 43kD endoglucanase. There is a homogeneous relationship.

When cleaning cotton mixed fabrics, the cleaning ability of the modified polyester described here can be demonstrated. To achieve this, the detergent composition should contain about 0.025 to 19% by weight of the detergent composition containing other ingredients. This purpose is achieved by placing the fabric in a cleaning solution.

Alternatively, the modified polyesters described herein can be used in the form of detergent additives during the wash cycle. may be added separately; this additive may be used as a dirt redeposition inhibitor, co-dispersant, etc. or other specific cleaning active materials such as cellulose enzymes; specifically listed here. Modified polyester can be used to pre-treat cotton blend fabrics before the main wash cycle of the laundry process. It can be used to

Optical brighteners are anionic, and their targets include disodium 4,41-bis(2-di- Ethanolamino-4-anilino-s-triazin-6-ylamino)stilbe N-2:21 disulfonate, dinathotium4. -4'-bis(2-morpholino -4-anilino-S-triazin-6-ylamilastilbene-2:21-dis sulfonate, disodium 4,41-bis(2,4-dianilino-S-triazid (6-ylamino)stilbene-2:21-disulfonate, monosodium 4.411-bis(2,4-dianilino-3-)riazin-6-ylamino)su Tilben-2-sulfonate, disodium 4゜41-bis(2-anilino-4 -(N-methyl-N-2-hydroxyethylamino)-S-triazine-6-y stilbene-2,2I-disulfonate, disodium 4,41-bisulfonate (4-phenyl-2,1,3-triazol-2-yl)-stilbene-2, 21 disulfonate, disodium 4,4' bis(2-anilino-4-(1- Methyl-2-hydroxyethylamino)-8-triazin-6-ylamino) stilbene-2　21-disulfonate, and sodium 2 (stilbene-2　1〜 Ru 411 (naphtho-1,2,4,5)-1,2゜3-triazole-211 - Sulfonates are included.

The granular inorganic perhydrate bleach contains 3 to 40%, preferably 8 to 25%, most preferably 8 to 25% by weight. Preferably it is used in an amount of 12 to 20% by weight based on the weight of the composition. preferable Bleach targets include sodium perborate monohydrate and tetrahydrate, and Beryl carbonate. Salts, and mixtures thereof are included.

Examples of other ingredients that may be mixed separately include peroxides, commonly referred to as bleach activators. There is a ruboxylic acid bleach precursor, which is present in granular detergents in the form of small spherules or aggregates. It is best to add it in the form. Peroxygen yarn bleach is preferably used in combination with a bleach activator. , thus the cleaning process of peroxyacids in aqueous solution (i.e. corresponding to bleach activators) Enables on-site generation at An example of a suitable compound of this type is British Patent No. 15 No. 86769 and No. 2143231 disclose that it is formed into small spheres. The method is described in European Published Patent Application No. 0062523. preferred compound For example, the tetraacetyl ether described in U.S. Pat. No. 4,818,425 ethylenediamine and sodium 3,5.5-trimethylhexanoyloxybenzene Diperoxide dodecanoic acid is also described in U.S. Pat. No. 42,592. Nonylamides of peroxyadipic acid disclosed in No. 01 and EPA Application No. 91. n-nonanonyloxybenzenesulfone-1-(N OBS), and acetyltriethyl citrate.

Bleach activators are usually used, for example from 0.5 to 10% by weight, often from 1 to 8% by weight, preferably Alternatively, it can be used in the composition of the present invention in an amount of about 2 to 6% by weight.

Optional other ingredients include bubble suppressants such as silicones, and silica silicone. There is a ricone mixture. Silicones are generally alkylated polysiloxane materials. Silica is commonly referred to as “silica aerogel” and “xerogel” (what (trade name) and various lipophilic silicas are used as fine powder products. It will be done. These materials may be added in particulate form, and this form of bubble suppressant is water-soluble, or water-dispersible and can be easily and freely added to substantially non-surfactant-impermeable carriers. . Alternatively, bubble suppressants can be used dissolved or dispersed in a liquid carrier; Then, it can be sprayed onto one or more other components by a spray method.

Useful silicone foam suppressants include the types of alkylated siloxanes and Consists of a mixture with solid silica. Such a mixture is capable of dispersing silicone onto a solid silica surface. Prepare by fixing on. Among the preferred silicone bubble suppressants are lipophilic silanes. (preferably trimethylsilanated) silica with a particle size range of 10 mm. It has a specific surface area of about 50 m2/g, and is made of silicone. When the weight ratio of silane to silanized silica is about 1=1 to about 1=2, the molecular weight is about 500 to about 500. Those obtained by intimate mixing with dimethyl silicone fluids ranging from about 200,000 to about 200,000 It is.

Examples of preferred silicone bubble suppressants are disclosed in U.S. Pat. No. 3,933,672. Ru. Other particularly useful bubble suppressants are described in West German patent application DTO 8 2646126. (dated April 289, 1977). Kaka An example of such a compound is the product name rDC-54 from Dow. It is a siloxane/glycol copolymer commercially available as 4J.

The usual concentrations of the above bubble suppressants are 0.001 to 2% by weight of the composition; Preferably it is 0.01 to 1%. This bubble suppressant can be added separately in particle form. It is preferable to add C fatty acids and microcrystalline wax. , and allows the inclusion of ethylene oxide/propylene oxide polymer copolymers do.

If not, these should adversely affect the dispersibility of the matrix. Ru. A technique for forming such bubble suppressant particles is the Baltrota (Ba+1o It is disclosed in US Pat. No. 3,933,672 to loNal et al.

Fabric softeners can also be added to the detergent compositions of this invention.

These softeners come in inorganic and organic types. British patent for inorganic softener It is described in Application No. 400898.

Examples of organic softeners for textiles include the water-soluble softeners described in UK patent application no. 400,898. Tertiary amines are included and described in UK Patent Application No. 1514276 and European Patent No. B Included are the water-insoluble tertiary amines disclosed in 0O11340.

A mixture of these and mono-0 quaternary ammonium salt is EPA-B No. 0026527 EPA-B No. 0026528, and di-long chain amides are EPA-B No. 024291. There is a disclosure in issue 9. Other useful ingredients for textile softeners include high molecular weight Polyethylene oxide material (EPA No. 0299575, EPA No. 0313146) ) are included.

The proportion of smectite (montmorillonite) clay in the granular detergent compositions described herein The proportion is usually 5 to 20% by weight, preferably 8 to 15% by weight (based on dry composition). It is. The water-insoluble tertiary amine or di-long chain amide material is typically 0.5 to 5% by weight. Usually 1 to 3% by weight, while high molecular weight polyethylene oxide and water-soluble cationic material The content of these ingredients is 0.1 to 2% by weight, usually 0.15 to 1.5% by weight. child These materials are typically added to the spray-dried portion of the composition and are or as a melt on other solid components of the composition. Both are easy.

Dye transfer inhibitors may be present in the composition, such as polyesters having a molecular weight of 5,000 to 2,200. Vinylpyrrolidone and the like can be added to the granular composition. The amount added is based on the amount of polyvinyl vinyl in the cleaning solution. The amount is such that the concentration of nilpyrrolidone is 5 to 500 mg/L. PVPV I can also be used as a dye transfer inhibitor.

The chelating agent (heavy metal ion sequestering agent) is also 0.05 to 5% by weight, preferably 0.05% to 5% by weight. 05 to 1% by weight, more preferably 0.1 to 0.5% by weight. Also included.

Among the suitable chelating agents is ethylenediamine-N1N-disuccinic acid (EDD). S), its alkali metals, alkaline earth metals, ammonium, substituted ammonium Salts or mixtures thereof are included. Preferred EDDS compounds are free acid and sodium or magnesium salts. EDDS sodium hit Includes MgEDDS and Mg2 EDDS. These magnesium Most preferred is the use of salts.

Other chelating agents include aminoalkylene poly(alkylene phosphonates) , alkali metal ethane-1-hydroxydiphosphonate, nitrilotrimethylene Phosphonate, Ethylenediamine Tetramethylene Phosphonate, and Diethylene and tetramine pentamethylene phosphonate. This phosphonate component is either in the form of a free acid or an alkali or alkaline earth metal ion complex. Make it exist. The ratio of the metal ion to phosphonate compound is at least 1:1. (See U.S. Patent Application No. 4,259,200). These organic phosphonates It is preferably used in the form of gnesim salt. The phosphorus-containing chelate in the composition of this invention The amount of toning agent should be limited to a minimum or preferably all (not used, other additives may be added) Aminopolycarboxylates such as EDTA and HEDTA are used as rating agents. It is a chelating agent.

Manufacturing method The compositions of this invention can be used by dry mixing methods, spray drying methods, agglomeration and granulation methods, and It can be produced by various methods such as a combination of these methods. From known granular products by these methods Various bulk densities can be prepared, including so-called "concentrate" products. .

Example The following examples are merely illustrative, and the abbreviations of each component are as follows.

LAS: Linear dodecylbenzene sulfonate AS: Sodium salt/C alkyl Sulfate +4-15 TAS: Sodium salt/tallow alcohol sulfate FA4 E7: Fat a Alcohol (C) ethoxy 1-h (E, O, about 7 mol adduct) F　A　25E　3　・Fatty alcohol (C) ethoxy 1-1- (E, O, approx. 3 molar adduct) CAT: C12 alkyltrimethylammonium chloride C1ay: Smectai clay Zeolite A4: Zeolite 4A- with an average particle size of 1-10 micrometers Na salt 5KS-6: Crystalline layered silicate (Hoechst) AA/MA copolymer/acrylic Maleic acid/maleic acid copolymer PAA: polyacrylate polymer CMC: Carboxymethylcellulose Phosphonate: Ethylenediaminetetramethylenephosphonic acid/Na salt EDTA: Ethylenediaminetetraacetic acid/Na salt PBI: NaBO-HO TAED Tetraacetylethylenediamine PVP/Polyvinylpyrrolidone Siriket - To (R=n): S i ○ 2 / N a 20 = n Cellulase: the above 43kD bacterial species Amylase: rTe+mamyl 60TJ (product name) (Noyo) Pase: rLipolase 100T J (product name) (Novo) Rotease "5avinase 4T J (product name) (Nova) SS S: Bubble suppressant (silica/silicone mixture) All modified polyesters listed here The stell is defined in claim 2.

The manufacturing method is as follows. The method for preparing a specific polyester includes the following steps: All in a round bottom flask. of monomer and stirred at 18°C until a clear solution was obtained, then continued stirring for 24 hours. A process lasting 4 hours; the contents were transferred to a 1-L capacity round-bottomed flask and placed under vacuum for 4 hours. Heating to 200°C for 5 minutes, removing from flask and cooling; A process in which glassy solids are lightly crushed and used.

Example 1 A detergent composition was prepared consisting of the following ingredients.

FA45E7 2. 5 ZEOLITE 33 Sodium citrate 21 Sodium carbonate 3 Sodium sulfate 5 Modified polyester 0. 5 Wood with a range of stains such as granular stains, oil stains, enzymatic stains, and bleach stains A bundle of cotton and polycodone fabrics was washed with compact detergent of the above formulation. each Half the bundle with the above detergent and the other half with the same formula as above except without cellulase. Washed with one detergent. The test was conducted in 25°H (German hardness) water at 40°C, and all All tests were repeated four times.

Stain removal effectiveness was evaluated by comparison with control stains of each type that were pre-washed under the same conditions. . The compositions used for the control fabrics were modified polyester or cellulase-free formulations. was used.

The stain removal effect was evaluated using a well-known series of panel rating units by two judges as follows. Evaluation was made using the Fe (+chelc) scale.

1 = I think there is a difference between the two stains.

2- There is definitely a difference between the two stains.

3 = There is a big difference between the two stains.

4 = There is as much difference between the two stains as black and white.

Average data compared to the control fabric was calculated. Oil stains on polycodone materials The results were as follows.

Stain Superiority over Example 1 Composition versus contrast Contaminated motor oil +1.1# Artifact +0.5 zero Book full of significance Example 2 Bundles with a range of stains such as granular stains, oil stains, enzymatic stains, and bleach stains was washed with a detergent similar to the formulation described in Example 1. Half of the bundle is as described in Example 1 The detergent was washed with the same formulation except that it did not contain modified polyester. . The washing conditions for these bundles were 40°C and 25H0, and each test was repeated 4 times. , samples were ranked according to stain removal (%). This calculation is performed using the known 1ab system. It was performed on a color spectrometer (McBelhg) using a stem. degeneration The concentration of polyester in the composition was varied between 0.025 and 10% by weight. Further tests were conducted. The results were as follows.

Density (%) 0.025 0.1 0.5 10 Average stain removal (%) (Oil on Polycodone) 5264 69 73 Examples of typical oil stains include contamination modes. Includes tar oil, shoe polish, and artificial stains.

Example 3 Improved oil stain removal by combining modified polyester and CMC Polycodone fabric swatches were prewashed several times with the CMC-containing detergent composition.

The purpose of this is to provide a history of CMC deposition on the fabric. Then dry and remove dirt. Stained with dyed motor oil (DMO). Half of the bundle was prepared similar to that described in Example 1. A control example was washed with a detergent composition, and the other was the same except that it did not contain modified polyester. Cleaned with prescribed detergent.

Calculate the stain removal (%) from each tracer using a Hunter colorimeter and switch ( (multiple) rankings. Also includes all data, dirt release polymers, Switch treated in a detergent with exactly the same formulation as above but without CMC compared with the number). The results are as follows: Test conditions: 40°C/25°H water - repeated 4 times Example 4 A pretreatment solution composition was prepared according to the following formulation.

Modified PE O, 51, 03, 05, 06, 06, 0 LAS 40 5 [1757 5- FA45E7 13 17 17-30 22 copolymer 46.5 32 5.0 20 64 72 Modified PE: Modified polyester Contaminates motor oil, sunburn, lotions, artificial and lipstick etc. A series of oil-based stains Pre-stained polycodone fabrics were pre-treated with all solutions prior to washing. Ta.

All woven fabrics pretreated with this formulation showed significantly lower stains from polycodone compared to untreated stains. The punching effect was significantly improved.

A compact detergent composition was prepared according to the following formulation.

Compact detergent 1 composition (ffiJ11%) polypeptide 4.00 -- 2 ．． QO2,00 Phosphonate) 0.19 1.00 -- -- 1.00 -- −　−−　−−EDT＾　−−−−0, KO2　0.12　−−　−−　−−　− -Na° carbonate/m carbonate 100 2.50 LO, OO10,0010,0 09,0010,0010,00 Silicate (R21 CMC], 00 2.00 2.50 2.50 2.50 ko, 50 ko, 5 0 ko, 50C1ay ++ o, so -----0,500,)O----P BI ----8,608,60---1---Bell carbonate---1 1,50--12,00--12゜0012.00TAED　----12 ,00--23,00----Protease---3,20--4,006 , OQ 4.00 4.00 Cellulase 1.20 1.60 1.40 1. 40 1.40 1.40 1.40 1.40 S-ze 0.50 -- 0. 30 0.10 0.10 0.10 0.10 0.10 Amylase 0.4 0 0. :10 0. KoOO, :10 0.10 0. )OO, :10 0.1 ON a 1 inch salt 0.20 0.10 ----1 ---------- Cross section (up to 100%) Example 5 Enhanced oiliness by combined use of modified SRP and C25E3 (=AE3 in this example) stain removal The combination of SRP and C25E 3 can be used in Skip Microsystem (SMS) and Skip Commercially available products such as Skip Regulir were tested as controls.

Significant improvement results were obtained for oil stains: a) SMS Oil stain removal rate (%) A B C Control 5M5-equivalent loading amount (140g) rAriel Ulfrx-DJ +0.3%SRP, 40℃ -0,40 -[1,34-1,02srA+iel old 1ra-D J + 0.3%SRP++4.7%8 to 3.40℃ -0,16-0,21-1,06 "^+iel Ulfrx-D J +5%AE7,60℃ -1,13g - 1,66s n/s [^riel Ul+r! -D J +0.3%SPR60 ℃ -1,15s -1,70s -1,60srAriel Ulfrx-D J+8%^E3 nil AEi, 60°C-(1,41Q, (11n/s "^+i61 Ultra-D J +0.3%SRP+4.7%AE3.6 0℃ -0,10-0,49-Q, 44s A: Cotton, B: Polycotton, C: Poly Riester b) Skip Regular Oil stain removal rate (%) A B C Control (Skip Regola+) -215g v+ 140grA+iel Ultra-D J +4.72AE3. 40℃ -0,57-0,71s -1,86srA+1el-Ult+1-D J +0.3%SRP -0, 260,230,83g+4.7%AE3. 40℃ In comparison with Skip Regular, SRP+AE 3 shows better results than AE3 alone. This is not the case with SMS.

Addition of AE3 improves the effectiveness against oil stains.

When AE3 and SRP are added together to ``^riel Ultra-DJ'' 1) Improve AE3 performance (vs. skip regular) or Either I) There is no improvement effect on AE3 alone (vs. 5M5) .

Example 6 Background of synergy with SRP nonionic C25E3 (=AE3) The surface of granular polypropylene material is extremely lipophilic and does not attract oily stains such as DMO. and capture it promptly.

conclusion The effect of SRP on cleaning granular polypropylene depends on the SRP:surfactant ratio There is.

1) Cleaning effectiveness is improved when the ratio of SRP to surfactant is low. SRP : If the surfactant ratio is high, the cleaning effect will be reduced.

0.025gSRP15g person riel O,05g5RP/3gA+1elSR P:Nl surfactant ratio (1:6 0.6) (1・2 0.2) Ho 0 Lip 0 Pyrene stains Clean stains Severe stains Dirt 2) Limitations for this phenomenon The critical factor lies in the presence and type of nonionic surfactants. surfactant and water alone gives dirty granular polypropylene as does SRP and water alone .

SRP concentration PPM 0 50 100 0 0 Product quantity I’l’M Q (l 0 60QQIOQOQ Degree of dirt: Severe dirt, dirt, severe dirt, dirt, dirt 3) If SRP and nonionic rAr ie IJ is zero, give dirty woven fabric. I can do it.

SRP beast PPM 0 50 0.50 Nonion concentration PPM Q rJ 5G0 5GO product concentration PPM 10000 10000 1f1000 10000 Degree of dirt Dirt Dirt Cree 4) C25A E 3 nonion enhances the cleaning effect and further enhances the SRP effect. Melt.

SRP concentration PPM 0 5G Nonion concentration PPM 500AE3 500AE3 Product concentration PPM 10001 1 Level of 10,000 dirt Clean Extremely clean 5) Synergy with Nonion When SRP and C25E3 are used for pre-treatment and cleaning of polyester woven fabrics This also extends to improvements in cleaning shoe polish.

Shoe polish removal rate (%) Ariel UN+z Ariel 45E7 Ariel ＾riel+0. 5%3.26%45E? +0.5%SRP +3.26%C25E3 SRP +3.26%C25E329 28 35 44 (remarkable) When SRP and nonionic (AE3) are used together, a synergistic effect can be obtained, and the effects are as follows. It depends on the SRP ratio to nonionic (AE3).

SRP: Nonionic ratio effect 1:20 Ant (but slightly reduced) Example 7 Attempts to thicken C25E3 with a variety of different detergent ingredients have been largely unsuccessful. Ta. Using the modified polyester of this invention provides a method for thickening C25E3. be done.

C25E 3 and stain-removing polymer in a ratio of 1:0.3 parts at room temperature while stirring lightly. When mixed, it forms a white viscous paste that does not separate even if left standing.

- Different soil release polymers provide the same thickening effect.

- Higher amounts of soil release polymer give a thicker paste.

ratio C25E 3 Dirt release polymer thickening effect (separation after standing) 1.0.3 Stable white paste 1 2.0 Stable white paste conditions: Room temperature, stirring gently Nonionic surfactant 025E 3 is added with the stain-removing polymer solution described in the present invention. It can be seen that the viscosity is increased.

The above facts suggest a method for granulating C25E3.

Continuation of front page (51) Int, C1,6 identification symbol Internal office reference number C11D 17106 9546-4HD06M 151507 (81) Designated countries 0A (BF, BJ, CF, CG.

CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AU, BB, BG, BR, BY, CA, CZ, FI, HU, JP, KP, K R, KZ, LK, MG, IIN, MW, NO, NZ, PL, RO, RU, SD .

SK, UA, US, VN FI (72) Inventor: Williams, Timothy, Avon, Newcastle, UK Tyne, Peachwood, Avenue, Bosquoise, 11

Claims (11)

[Claims] 1. Modified polyester compound, and addition of 2 to 5 moles of ethylene oxide C8- consisting of a nonionic surfactant selected from 18 primary alcohol ethoxylates. A detergent composition, wherein the modified polyester compound is dimethyl terephthalate, Dimethyl sulfoisophthalate, ethylene glycol, and 1,2-propane It is a random copolymer of diols, and most of its terminal groups are sulfobenzoate. and secondarily a monoester of ethylene glycol and/or propanediol. A detergent composition comprising Stell. 2. The nonionic surfactant is a C12-15 primary compound with about 3 moles of ethylene oxide added thereto. A detergent composition according to claim 1, consisting of an alcohol ethoxylate. 3. The ratio of the nonionic surfactant to the modified polyester is 1:0.3 to 1:2. 3. The detergent composition according to claim 2, wherein the detergent composition is 0. 4. Dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glyco terminal groups of random copolymers obtained from 1,2-propanediol and 1,2-propanediol. consists mostly of sulfobenzoates and secondarily ethylene glycol and/or or a modified random copolymer consisting of a monoester of propanediol. A polyester compound is added with 2 to 5 moles of ethylene oxide and a C8-18 primary alkali. Consists of combined use with nonionic surfactants selected from coal ethoxylates , a method of using a modified polyester compound, the method comprising: applying a fabric to an aqueous laundry solution containing said compound; said modified substance for use as a cleaning agent to remove oil-based stains from said fabric by contacting with said fabric. Usage of polyester compounds. 5. The compound contains about 46% by weight of dimethyl terephthalate, about 16% by weight of propylene pan-1,2-diol, about 10% by weight ethylene glycol, about 13% by weight Contains sulfobenzoic acid and about 15% by weight sulfoisophthalic acid, and The method according to claim 4, wherein the molecular weight is 2500 to 3500. 6. The nonionic surfactant is a C12-15 primary alkali containing about 3 moles of ethylene oxide. 6. The use according to claim 4 or 5, which is a coal ethoxylate. 7. The ratio of modified polyester to nonionic surfactant is 1: to 1:20. The method of use described in any one of claims 4 to 6. 8. 8. According to any one of claims 4 to 7, said compound is used in combination with a cellulase enzyme. Usage as described. 9. The compound is added to a detergent composition containing other detergent ingredients at a concentration of 0.025 to 10% by weight. 9. The method according to any one of claims 4 to 8, which is used by adding in a range of %. 10. The above compound is used by adding it to a detergent additive composition for pre-cleaning woven fabrics. , the use according to any one of claims 4 to 8. 11. Apply the detergent composition at the beginning of the wash cycle or at the start of the pre-wash cycle. The detergent composition is stored in a container with a structure that allows it to be released, and the cleaning and/or preparatory Claim in which the container is placed in a drum of a washing machine together with the fabric to be washed. 9 or 10.