JP2003505578A - Cloth protection treatment composition and cloth treatment method - Google Patents

Abstract

  (57) [Summary] A fabric protection system comprising a radical photoinitiator selected from a hydrogen abstraction type photoinitiator, a tie layer exfoliated radical photoinitiator or a mixture thereof treats the fabric during the washing or rinsing stage of the fabric in the washing process. For example, it is used as a stain removal system. The fabric treatment system can be incorporated into the fabric cleaning composition or conditioner composition.

Description

Detailed Description of the Invention

The present invention relates to a fabric protective treatment composition comprising a novel treatment system for stain removal without discoloration. The invention also relates to a method of treating fabrics using a novel treatment system that removes stains without discoloring. The invention further relates to the use of the novel treatment system for stain removal without discoloration, for the protective treatment of fabrics.

BACKGROUND OF THE INVENTION The present invention relates to the treatment of fabrics after the use of the fabric, and in particular to the treatment of the fabric to recover it from the quality degradation resulting from the use of the fabric, such as stains and stains. Such treatment is hereinafter referred to as cloth protection. Cloth protective treatments include laundry and the use of non-detergent based fabric protective products such as spray products. Ingredients included in fabric protection compositions for the purpose of color fading prevention have received considerable attention. These components include, for example, dye transfer inhibitors, stain removers, photobleaching inhibitors, and fluorescence inhibitors.

European patent application no. 97200107.7 discloses a laundry detergent composition containing a specific polymer system to provide a stain removal effect. International patent application no. PCT / EP97 / 07289 discloses a fabric treatment composition comprising a sunscreen material which prevents fading by sunlight. International patent WO 95/13354
Disclosed is a composition comprising PVPNO as a dye transfer inhibitor and a polymer such as an N-vinylpyrrolidone / N-vinylimidazole copolymer. European patent publication EP
-A-0035470 discloses a fiber treatment composition containing a photobleaching component. The photo-bleaching material has some effect on the spots, but it also acts on the dye.

The inventors of the present invention sought suitable alternative treatment ingredients that could be included in the fabric protective composition for stain removal without discoloration.

The inventors of the present invention have found that a radical photoinitiator system that acts by a hydrogen abstraction mechanism or a tie layer stripping mechanism can act as a stain-bleaching component in a fabric protective composition. I found out.

Radical photoinitiators are known per se and are used in fields not related to the invention, such as the polymerization reactions of materials, the crosslinking reactions of polymers and the curing reactions.

DEFINITION OF THE INVENTION Accordingly, the present invention provides a fabric protection composition comprising a radical photoinitiator selected from hydrogen abstraction type radical photoinitiators, tie layer exfoliation type radical photoinitiators and mixtures thereof. To do.

The present invention further provides a method of protective treatment of a fabric comprising treating the fabric with a radical photoinitiator selected from hydrogen abstraction type radical photoinitiators, tie layer exfoliation type radical photoinitiators and mixtures thereof. provide.

The present invention further proposes the use of a radical photoinitiator selected from a hydrogen abstraction type radical photoinitiator, a tie layer exfoliation type radical photoinitiator and a mixture thereof in a method for protective treatment of cloth.

It has been found that the radical photoinitiators of the invention have the advantage of being stable in solution when stored in the dark. It has been found that these radical photoinitiators do not spontaneously degrade during storage.

Furthermore, it has been found that the radical photoinitiator of the present invention acts on spots without the need for agitation. The advantage obtained by this is that it can be used by a simple coating method. Further, damage to the cloth such as fibrillation (defibration) can be prevented.

It has been found that the radical photoinitiator system of the present invention is soluble or dispersible in media other than water and can be used in apparel limited to dry cleaning.

Finally, it has been found that the radical photoinitiators of the invention have a bactericidal effect.

[0014]     (Detailed explanation)   Radical photoinitiator   Suitable radical photoinitiators that can be used in the present invention include one of the following routes:
When excited by light, it is a component that produces radicals that can attack spots on the cloth.

[0015]   Hydrogen abstraction   The hydrogen abstraction type radical photoinitiator has the following reactions:

[0016]

[Chemical 1] [Wherein X represents a radical photoinitiator and RH represents a hydrogen donating compound].

Suitable examples of the hydrogen abstraction type radical photoinitiator X include benzophenone, acetophenone, pyrazine, quinone and benzyl.

Suitable examples of hydrogen donating compounds R—H include organic molecules containing aliphatic C—H groups, examples of which include propan-2-ol and a cellulose, polyester or nylon backbone. It is a compound.

K (1) is the rate constant of the hydrogen abstraction reaction. When RH is propan-2-ol, the rate constant k (1) is preferably greater than 10 ⁴ mol ⁻¹ 1s ⁻¹ .

[0020]   Bonding layer exfoliation type radical photoinitiator   The tie-layer exfoliated radical photoinitiator has the following reactions:

[0021]

[Chemical 2] [Wherein k (2) represents the rate constant of the bonding layer peeling reaction]. Preferably k (2) is greater than 10 ⁶ s ^-1 .

Suitable tie layer exfoliating radical initiators may be selected from the following group: (A) Alpha amino ketones, especially alpha amino ketones containing a benzoyl moiety, which is also referred to by another name as alpha-aminoacetophenone, eg 2-methyl-1-
[4-phenyl] -2-morpholinopropan-1-one (trademark Irgacure
907), (2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trademark Irgacure 369). (B) Alpha hydroxyketones, especially alpha-hydroxy-acetophenone, e.g. 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one) (Trademark Irgacure 295
9), 1-Hydroxy-cyclohexyl-phenyl-ketone (trademark Irgacu
re 184). (C) Phosphorus-containing photoinitiators such as monoacyl and bisacylphosphine oxides and sulfides, eg 2-4-6- (trimethylbenzoyl) diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl- Phosphine oxide (Trademark Irgacure 819). (D) Dialkoxy acetophenone. (E) Alpha-haloacetophenone. (F) Trisacylphosphine oxide.

Suitable radical photoinitiators are international patents WO9607662 (trisacylphosphine oxide), US patent US5399782 (phosphine sulfide), US
541060, European Patent Publications EP-A-57474, EP-A-73413 (
Phosphine oxide), EP-A-0888050, EP-A-0117233,
EP-A-0138754, EP-A-0446175 and US patent US455.
9371.

Suitable hydrogen abstraction-type photoinitiators are, for example, European Patent Publication EP-A-0003002 in the name of Ciba Geigy, EP-A-04 in the name of Ciba Geigy.
46175, British patent GB2259704 (alkylbisacylphosphine oxide) in the name of Ciba Geigy, US Pat. No. 4,792,632 (bisacylphosphine oxide), US patent US555466 in the name of Ciba Geigy.
3 (alpha-aminoacetophenone) and US Pat. No. 5,767,169 (alkoxyphenyl-substituted bisacylphosphine oxide).

The radical photoinitiator is based on A. F. Cunningham, V.I. Desorby,
K. Dietliker, R .; Husler and D.H. G. Leppard
, Chemia 48 (1994) 423-426.

Without wishing to be bound by theory, it is preferred that all radical photoinitiators react via an excited triplet state in order to reduce the effects of the cage effect.

Radical photoinitiators suitably undergo one of the reactions presented above when excited by radiation, generally in the range 290-800 nm. For example, natural sunlight, including light in this region, will adequately cause one of the reactions described above for radical photoinitiators. Preferably, the radical photoinitiator is in the ultraviolet range (290-400 nm
) Has a maximum extinction coefficient of greater than 100 mol ⁻¹ 1 cm ⁻¹ . Suitably the radical photoinitiator is solid or liquid at room temperature.

Suitably the radical photoinitiator is substantially colorless and a colorless photoproduct is obtained when one of the reactions presented above occurs.

Preferably the composition is for example European Patent Publication EP-A-0088050, EP-
Sensitizers such as thioxanthone described in A-0138754.

[0030]   Preferred radical photoinitiator system   The inventors of the present invention have a certain hydrophobicity as measured by the log P value.
It has been found that the radical photoinitiators that are used have particularly favorable effects. Remove stains
All materials intended to be used also have the property of attacking dyes. Preferred
The radical photoinitiator system has an excellent balance of stain removal effect and dye aggressiveness.
ing.

Preferably, the radical photoinitiator has a high log P value. Here lo
g P is the octanol-water partition coefficient. It is preferred that the radical photoinitiator has a log P measured at 25 ° C. of greater than 2.5, more preferably greater than 4.0.

[0032]   Cloth protection composition   The present invention relates to an industrial or household cloth laundry composition and a cloth conditioning composition.
And a cloth washing and conditioning composition (so-called detergent-introducing type (thro
Suitable for use in a ugh the wash) conditioner composition)
It The present invention also relates to non-detergent based fabric protection compositions for industrial or domestic use, such as
, Can be used in spray compositions.

[0033]   Cloth laundry composition   The fabric laundry composition according to the present invention may be in any suitable form, eg powder form, compression molding.
It may be in the form of a powder detergent, a liquid detergent or a solid bar detergent.

The laundry laundry composition of the present invention is a laundry laundry selected from non-soap anionic surfactants, nonionic surfactants, soaps, amphoteric surfactants, zwitterionic surfactants and mixtures thereof. Including detergent material.

Suitable anionic surfactants are known to the person skilled in the art and include alkylbenzene sulfonates, primary and secondary alkyl sulphates, especially C ₈ -C ₁₅ primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates. Alkyl xylene sulfonates, dialkyl sulfosuccinates; ether carboxylates; isethionates; sarcosinates; fatty acid ester sulfonates and mixtures thereof. Sodium salts are generally preferred.

Nonionic surfactants are also known to those skilled in the art, and are primary and secondary alcohol ethoxylates, especially C ₈ -C ₂₀ fats ethoxylated with an average of 1-20 moles of ethylene oxide per mole of alcohol. family alcohols, more particularly aliphatic primary and secondary alcohols of C _{1 0} -C ₁₅ ethoxylated with an average 1-10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamides). Mixtures of nonionic surfactants may be used.

Suitable detergent compositions that may be used in household or industrial fully automatic cloth washing machines are generally anionic non-soap surfactants or nonionic surfactants, or as known to those skilled in the art. A suitable mixture of both surfactants in appropriate proportions, optionally with soap.

Many suitable detersive active compounds are available, eg “Surface-A”.
ctive Agents and Detergents ", Volumes
I and II, Schwartz, Perry & Berch.

The anionic surfactant is suitably 5% by weight-50% based on the fabric treatment composition.
It is present at a level of weight%, preferably 10-40% by weight. The nonionic surfactant is suitably present at a level of 1-20% by weight, preferably 5-15% by weight.

The total amount of surfactant present depends on the intended end use, and may be present in as much as 60% by weight in the fabric hand-washing composition. Amounts of 5-40% by weight are generally adequate in machine-washing fabric compositions.

[0041]   Detergency builder   The detergent compositions of the present invention generally further contain one or more detergency builders.
Will. The total amount of detergency builder in the composition is 5-80% by weight, preferably 10
-60% by weight may be suitable.

Inorganic builders that may be present include British Patent GB 1,437,950 (Uni
sodium carbonate, if desired in combination with calcium carbonate crystallization seeds as disclosed in Lever); crystalline and amorphous aluminosilicates, eg
Zeolites as disclosed in GB 1,473,202 (Henkel) and crystalline / amorphous aluminosilicate mixtures as disclosed in GB 1,470,250 (Procter &Gamble); European Patent EP16451.
There are layered silicates such as those disclosed in 4B (Hoechst). Inorganic phosphate builders such as sodium orthophosphate, sodium pyrophosphate and sodium tripolyphosphate may also be suitably used in the present invention.

The detergent composition of the present invention preferably contains an aluminosilicate of an alkali metal, preferably sodium, as a builder. Sodium aluminosilicate is generally included (on an anhydrous basis) in an amount of 10-70% by weight, preferably 25-50% by weight.

[0044]   Alkali metal aluminosilicates can be crystalline, amorphous or a mixture of both.
General formula:       0.8-1.5Na_TwoO. Al_TwoO_Three． 0.8-6 SiO_Two Can have

These materials contain some bound water and contain at least 50 mg C
It is required to have a calcium ion exchange capacity of aO / g. Preferred sodium aluminosilicates contain SiO ₂ units of 1.5-3.5 (in the above formula). Both amorphous and crystalline materials can be readily prepared by the reaction of sodium silicate and sodium aluminate. This reaction is well documented in the literature.

A suitable ion exchange detergency builder consisting of crystalline sodium aluminosilicate is, for example, British Patent GB 1,429,143 (Procter & Gamble).
)It is described in. Preferred sodium aluminosilicates of this type are the commercially available known zeolites A and X, and mixtures thereof.

The zeolite may be the commercially available zeolite 4A, which is currently widely used in laundry powder detergents. The zeolite builder contained in the composition of the present invention is European Patent EP38.
It may be Maximum Aluminum Zeolite P (Zeolite MAP) as described and claimed in 4070A (Univer). Zeolite MAP is 1.
33 or less, preferably in the range of 0.90 to 1.33, more preferably 0.90-
It is defined as a zeolite P type alkali metal aluminosilicate having a silicon to aluminum ratio in the range of 1.20.

Zeolites MAP having a silicon to aluminum ratio of 1.07 or less, more preferably about 1.00 are particularly preferred. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO / g anhydrous material.

Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic / maleic copolymers and acrylic phosphinates; citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxys. Polycarboxylate monomers such as methyloxysuccinate, carboxymethyloxymalonate, dipicolinate, hydroxyethyliminodiacetate, alkyl- and alkenylmalonates and succinates; and sulfonated fatty acid salts. This list is not an exhaustive list of organic builders.

Particularly preferred organic builders are 5-30% by weight, preferably 10-25% by weight.
Citrate used in a suitable amount of 0.5-15% by weight, preferably 1-10% by weight of an acrylic polymer, more particularly an acrylic / maleic copolymer.

Both inorganic and organic builders are preferably present in the form of alkali metal salts, especially sodium salts.

[0052]   Bleaching ingredients   The detergent composition of the present invention also provides a peroxy bleach that can generate hydrogen peroxide in aqueous solution.
Whitening systems, such as inorganic persalts or organic peroxy acids, may optionally be included.

Suitable peroxy bleach compounds include organic peroxides such as urea peroxide,
And inorganic persalts such as alkali metal perborate, percarbonate, perphosphate,
There are persilicates and persulfates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate and sodium percarbonate.

Particularly preferred is sodium percarbonate which has a protective coating which prevents destabilization due to humidity. Sodium percarbonate with a protective coating consisting of sodium metaborate and sodium silicate is disclosed in British Patent GB 2,123,044B (Kao).

The composition may further contain a photobleaching system, for example as described in EP-A-0035470.

[0056]   Fabric softening composition   The fabric treatment composition of the present invention may be a fabric conditioning composition or a fabric conditioner.
It may also include a positioner.

[0057]   Cloth softener compound   The fabric softener compound is preferably a cationic, nonionic or anionic fabric softener.
It is a softener compound.

The fabric softener compound may be a quaternary ammonium material containing a polar head group and one or two alkyl or alkenyl chains. The fabric softener compound may also be a non-ionic fabric softener compound such as a fabric softening oil, or a fabric softening silicone composition or a fabric softening ester composition such as a sugar ester.

Particularly preferably, the fabric softener compound has two long chain alkyl or alkenyl groups having an average chain length longer than C ₁₄ , more preferably each chain is longer than C _14. It has an average chain length, more preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of C ₁₈ .

It is preferred that the long chain alkyl or alkenyl groups of the fabric softener compound are predominantly linear.

It is highly preferred that the fabric softener compound is substantially water insoluble. A fabric softener compound that is substantially insoluble in the context of the present invention is a fabric softener compound having a solubility of less than 1 × 10 ⁻³ wt% in deionized water at 20 ° C., preferably less than 1 × 10 ⁻⁴ wt%. A fabric softener compound having a solubility of 1, most preferably 1 in deionized water at 20 ° C.
It is defined as a fabric softener compound having a solubility of ^{x10 -3} -1 x 10 ^-6 .

[0062]   formula:

[0063]

[Chemical 3] [Wherein R ¹ and R ² represent a hydrocarbyl group having 12 to 24 carbon atoms, R ³ and R ⁴ represent a hydrocarbyl group containing 1 to ⁴ carbon atoms, and X is an anion, preferably Representing an anion selected from a halogen group, a methylsulfate group and an ethylsulfate group], quaternary ammonium compounds of the known type which are substantially water-insoluble and are preferred.

Representative examples of these quaternary softeners are di (tallowalkyl) dimethylammonium methylsulfate, dihexadecyldimethylammonium chloride, di (hydrogenated tallowalkyl) dimethylammonium chloride, dioctadecyldimethylammonium chloride, Di (hydrogenated tallow alkyl) dimethylammonium sulfate, dihexadecyldiethylammonium chloride, di (coco palm alkyl) dimethylammonium chloride, ditallowalkyldimethylammonium chloride and di (hydrogenated tallowalkyl) dimethylammonium chloride (
Trademark Arquad 2HT).

Another preferred softener contains ester or amide bonds, eg Ac
It is available under trademarks such as soft 580, Varisoft 222 and Stepantex.

A particularly preferred fabric softener compound is a water insoluble quaternary ammonium material consisting of a compound having two C _12-18 alkyl or alkenyl groups attached to the molecule via at least one ester bond. is there. More preferably, the quaternary ammonium material has two ester bonds. Preferred ester linked quaternary ammonium materials that can be used in the present invention have the formula:

[0067]

[Chemical 4] Can be represented by, in the formula, each of ^{R 1} group is independently selected from _{C 1-4} alkyl group, hydroxyalkyl group or a _{C 2-4} alkenyl group, each ^{R 2} group is independently _{C 8-} Selected from ₂₈ alkyl or alkenyl groups, where T is

[0068]

[Chemical 5] , X ⁻ represents an appropriate arbitrary anion, and n represents an integer of 0-5. Di (ethyl ester) dimethyl ammonium chloride (DEEDMAC) is particularly preferred.

[0069]   A second preferred type of quaternary ammonium material has the formula:

[0070]

[Chemical 6] [Wherein R ₁ , n, X ⁻ and R ₂ have the same meanings as defined above].

[0071]   It is advantageous for environmental reasons if the quaternary ammonium material is biodegradable.

Preferred materials of this class such as 1,2-bis [cured tallowyloxy] -3-trimethylammonium propane chloride and their method of preparation are described, for example, in US Pat. No. 4,137,180 (Lever Brothers). ing. Preferably these materials contain minor amounts of the corresponding monoesters such as those described in US Pat. No. 4,137,180, eg 1-cured tallowyloxy-2-hydroxytrimethylammonium propane chloride.

The fabric softeners can also be polyol ester quats as described in EP 0 638 639 (Akzo).
t, PEQ).

[0074]   Other ingredients   The composition of the present invention also comprises a pH buffering agent, a perfume carrier, a fluorogenic agent, a coloring agent, a hydrous agent.
Tropes, foam suppressors, anti-settling agents, enzymes, optical brighteners, opacifiers, shrink-proofing agents, wrinkle-preventing agents
Agents, anti-spot agents, bactericides, fungicides, preservatives, drape imparting agents, antistatic agents and
And one or more optional ingredients selected from ironing aids.

The present invention may be in the form of a dilute or concentrated aqueous solution or suspension, for example as described in WO 97/15651, WO 95/27769. Alternatively, the fabric softening composition may be in the form of a powder that can be used in the rinse cycle of a fully automatic washing machine. Alternatively, the fabric softening composition may be, for example, International Patent WO95 / 2777.
It may also be in the form of a sheet of a fabric conditioning composition that can be used in a tumble dryer, as disclosed in No. 7. Alternatively, the fabric conditioning composition may be in the form of a substantially non-aqueous concentrate as described in International Patent Application PCT / EP99 / 00497.

The laundry detergent composition according to the present invention may further comprise a detergent-type softener, such as a cationic fabric softener.

[0077]   Non-detergent based cloth protection products   The present invention can also be used in non-detergent based fabric protection products. For example, if the product is
A void system may be included as a main component. For example, a non-detergent-based composition may
Consists of a stain remover solution in a suitable solvent such as propanol, alcohol, etc.
Good. The composition may be an aerosol composition or a spray composition. The composition is
Stick-shaped, stick-shaped, or pressure applied to the surface by absorbing with a sponge
It may be in the form of a coating composition.

[0078]   The invention will be explained in more detail on the basis of the following non-limiting examples.

[0079]   Example   Unless otherwise specified, all amounts are percent by weight or parts by weight.

The following radical initiators are used in these examples. These are Ciba S
It is commercially available under the tradenames below from specialty Chemicals.

Irgacure 369-1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (log P
= 2.9, measured at 25 ° C).

Irgacure 819-bis (2,4,6-trimethylbenzoyl)
-Phenylphosphine oxide (log P = 5.8, measured at 25 ° C).

Irgacure 2959- (1- [4- (2-hydroxyethoxy)
-Phenyl] -2-hydroxy-2-methyl-1-propan-1-one (log
P = 0.84, measured at 25 ° C.).

[0084]   Example 1   Cloths with the types of stains listed in Table 1 were obtained from a supplier (Equest
, Aged for 3 days and then sealed). Next, a variety of stain cloths
With a solution of ethanol containing a radical photoinitiator of
Place in S3000 Weatherometer WOM ™ for 12 minutes
Held (irradiated at 340 nm with a power level of 0.35 w / m2). Spectra
The reflectance at 460 nm (measured using a flash SF60 ™ reflectometer (
The change in R (460 nm)) is shown in Table 4.

The following treatment scheme was used: Treatment 1-no soaking Treatment 2-Stained cloth is placed in ethanol, removed, dried, moistened with water and placed in a Weatherometer for 12 minutes.

Treatment 3—Place in ethanol containing 0.20% by weight of Irgacure 2959 ™, remove, dry, wet with water, place in WOM and hold for 12 minutes.

Treatment 4-Put into ethanol containing 0.20% by weight of Irgacure 819 ™, remove by drying, moisten with water and place in a Weatherometer for 12 minutes.

[0088]   The results are shown in Table 1.

[0089]

[Table 1]

Radical initiators generally increase the reflectance of various stains at 460 nm. That is, the radical initiator effectively removes stains from the cloth.

[0091]   Example 2   Except for varying the amount of Irgacure 819 ™ in ethanol.
The procedure of Example 1 was repeated using Reasons 1, 2 and 4. The results are shown in Table 2.

[0092]

[Table 2]

The results show that stains are eliminated by very low levels of radical photoinitiator based on the weight of the fabric.

[0094]   Example 3   To compare the effect of various radical initiator systems on stains and dyes, the following
An experiment was conducted. I bought a cotton cloth with various kinds of stains from the above-mentioned Equest
It was Various on the basis of cloth weight (on-weight-fabric, owf)
From ethanol to a spotted cloth by slamming a level of photoinitiator
Transferred. The ethanol was then evaporated, the cloth dampened with deionized water and Atla
Place in S3000 Weatherometer ™ and illuminate for 12 minutes
(Power = 0.35W / m^TwoIrradiation to 340 nm). Cloth with stains and 1
The reflectance of the stain-free cloth piece was measured at 460 nm, and the ΔE value was calculated. these
Values were compared to controls. The control was that the ethanol contained no radical initiator.
Except for and, the stains are treated in the same way. As in Example 1, the initiator was
Excellent stain-eliminating effect on curry, bolognese, β-carotene and chilli
It was found to have. Tables 3 and 4 show various levels based on the weight of the fabric.
Of Irgacure 2959 and 819.TM.
It is shown that the average decrease in ΔE of various stains was above the control.

To determine how much the initiator damages the dye, the above experiment was repeated using a print cloth purchased from Veebee The of Harrogate England, instead of the spotted cloth. In this case, the ΔE value represents dye damage. Sixteen different dyes were tested and the average dye damage measurements are shown in Tables 3 and 4.

[0096]   The following dyes were used.

[0097]

[Table 3]

The depigmentation measurement divided by the dye damage measurement gives the benefit / harm value.
This value represents how specific the initiator is for stains over the dye. Two
． Irgacure 819 ™, which has a log P of greater than 5, is 2.
It will be appreciated that it is much more highly spot-specific than Irgacure 2959 ™, which has a log P below 5. This is a low level (0-0
． 02% owf), and at this level Irgacure 819 (
Trademark) provides a strong stain removal effect, but very little dye damage.

[0099]

[Table 4]

[0100]

[Table 5]

Note that much lower dye damage was observed when the experiment was repeated using a dry cloth. However, the spot erasing effect also decreased.

[0102]   Examples 4 and 5   The following base powders were prepared:   Linear alkylbenzene sulfonate sodium (LAS) 23.60%   Sodium tripolyphosphate-19.22%   Sodium silicate-4.81%   Sodium sulfate-28.59%   Calcite (calcium carbonate) -10.30%   Trace component-1.08%   Water-12.49%

In Example 4, 1 gram of this base powder was added to 0.024 g of Irgacure.
Intimately mixed with 819. The final product is 2.3% by weight of Irgacure 819.
Contains. In Example 5, 1 gram of this base powder was added to 0.024 g of I.
Intimately mixed with rgacure 369. The final product is 2.3 wt% Irgac
It contains ure 369.

In each example, the mixture of base powder and radical photoinitiator was dissolved in 400 grams of water at 40 ° C. Three cotton cloth lots were prepared. Each lot contained a total weight of 16.1 grams of soft cotton and a total weight of 10 grams of brushed cotton. The cotton cloth was all white. For each lot, both types of cloth were cut into four pieces.
The lot was then washed for 5 minutes with the solution prepared above. A piece of soft cotton and a piece of brushed cotton were taken out and dried. The wash was discarded and the cotton cloth was rinsed with 600 grams of cold water. A piece of soft cotton and brushed cotton was taken out and dried. The first rinse was then discarded. A second rinse was then done with another 600 grams of water. A piece of soft cotton and a piece of brushed cotton were removed again.

In order to know the amount of the initiator adhering to the cloth, the strips of soft cotton and brushed cotton taken at each stage were tested. This measurement was performed by measuring the reflectance of the dry cloth at 320 nm using a Spectraflash SF60 ™ reflectance spectrometer. The following results were obtained.

[0106]

[Table 6]

[0107]

[Table 7]

In all cases, the reflectance of the fabric washed with the powder composition containing the radical initiator is lower than the reflectance of the fabric washed with the control composition containing no radical initiator. The reason is that the Irgacure radical initiator is strongly absorbed at 320 nm and reduces the reflectance. The measured reflectance change is significantly above the noise level of this type of measurement, demonstrating the attachment of the initiator.

Examples 4 and 5 demonstrate that radical photoinitiators can adhere to fabrics from laundry compositions.

[0110]   Example 6   The following rinse conditioner formulations were prepared:     HEQ¹    -4%     Fragrance-0.3%     Irgacure 819 ™ -0.66%     Water-up to 100%     1 HEQ = 1,2 bis [cured tallowyloxy] -3-trimethyla
Mmonium propane chloride, made by Hoechst

3 grams of this rinse conditioner was dissolved in 600 grams of cold water. 1
8 grams of cotton cloth was placed in this solution and held for 5 minutes. After this time, the cotton cloth was taken out and dried. The reflectance spectrum of the plain cotton was measured at 320 nm using a Spectraflash SF60 ™ reflectometer.

Calculated from the reflectance results provided about 0.003% (based on the weight of the fabric) of the radical photoinitiator.

[0113]   Example 7   Clothes with various types of stains can be found on the Veebee Tech. , Harlogat
e, purchased from England. 0.2% benzophene based on cloth weight
The ethanol was transferred to the spotted cloth by striking non. Next
Then the ethanol was evaporated. Dampen the cloth with deionized water and use Atlas S300.
0.3 per square meter in 0 Weatherometer ™
Irradiation at 340 nm with 5 watts for 30 minutes. Spectraflash SF6
Using a No. 0 Reflectometer (trademark), a cloth piece irradiated with stains and a piece of cloth without stains
The ΔE value was calculated by measuring the reflectance at 460 nm. These values were compared to controls
. Controls were treated similarly except that ethanol contained no radical initiator
Is. Next, 4 types of stains (Voronase, curry, beta carotene and chili)
For, the average increase without spots compared to the control was calculated. The average of these stains
ΔE was 5.3. It uses a hydrogen abstraction type radical photoinitiator
It shows that a certain level of stain removal can be obtained.

[0114]   Example 8   The following experiment is to test the effect of pH on the effect of radical photoinitiator.
went.

The procedure of Example 7 was repeated except that the ethanol was transferred to the spotted fabric by beating 0.1% Irgacure 819 ™ based on the weight of the fabric. Independent samples were taken for each stain and moistened with buffer solutions of different pH. The resulting fabric is Atlas S3000 ™ Weather.
It was put in an ometer and irradiated for 12 minutes. The change in average reflectance at 460 nm after the treatment is shown in the table. The average reflectance at 460 nm for the four treatments was 46.5. It will be appreciated that radical photoinitiators provide a substantial improvement in reflectance over a wide pH range.

[0116]

[Table 8]

[0117]   Example 9   Lucerin TPO-L (2,4) at 0.02 and 0.2% owf respectively
, 6-Trimethylbenzoylethoxyphenylphosphine oxide, manufactured by BASF
) And Irgacure 184 (1-hydroxy-cyclohexyl-phenyl
The experiment of Example 3 was repeated using-(ketone, Ciba). The result is
It shows in Table 8.

[0118]

[Table 9]

[0119]   Example 10   A white polyester cloth with stains (Veebee Tech) is used as a preceding example.
When treated with the same initiator as above, a superior cleaning effect over the control was observed. Dyeing
Little damage was observed with the colored polyester cloth.

[0120]   Example 11   Tomato paste (Traditional Ragu Recip) on Tenjiku cotton
e Van den Bergh foods, ingredients: tomato, sunflower oil, ta
Onions, salt, sugar, glucose, garlic powder, basil, parsley, spice extract
, Citric acid, basil, parsley, CaCl_Two) And aging in air for 1 day
The oily tomato stain was attached by doing. Linen the cloth with stains
And washed under the following conditions. 12g of cloth in each tank (6g of which is
Cloth), 240ml water, 0.34g borax, 1.44g liquid detergent
And washed at a temperature of 40 ° C. for 20 minutes and not rinsed. Tumble dryer
And dried in WOM and held for 6 minutes.

Liquid detergents include Coco 5EO (Clariant-nonionic surfactant), S
DS (sodium dodecyl sulfate-anionic surfactant), CTAC (cetyltrimethylammonium chloride-cationic surfactant), Arquad 2H
Prepared from T (Akzo Nobel-Cationic Surfactant), 0.1% Lucerin TPO-L, 10% ethanol, and a balance amount of water, based on the weight of the formulation. The amount of surfactant in each formulation is shown in the table.

[0122]

[Table 10]

The results are shown below. In all cases, the samples containing the initiator showed lower ΔE values than the control (better stain removal effect than the control).

[0124]

[Table 11]

[0125]   Example 12   Formulation of Example 11 using Irgacure 819 instead of TPO-L
The thing L1 was prepared. Excellent stain removal effect over the control was obtained.

[0126]   Example 13   15.3% anionic surfactant, 10% ethanol, 0.1% Luc
A detergent composition was prepared containing erin TPO-L and a balanced amount of water.
The anionic surfactants were LAS and SDS.

When these were tested in the wash protocol of Example 11, both showed a significant increase in the stain removal effect after irradiation compared to the water alone control. This indicates that the initiator in the wash was effective. Beneficial results were also observed with β-carotene and paprika stains.

[0128]   Example 14   Persil solution was purchased at Ireland and the product contained 0.01% by weight of Luce.
rin TPO-L was added. wash and rinse the β-carotene stain cloth
Upon irradiation, the stain removal effect was found to be much greater in the presence of the initiator.
Was done.

[0129]   Example 15   On a cotton cloth stained with β-carotene, an initiator, benzoin, dimethoxypheny
Luacetophenone, benzoin methyl ether and benzoin ethyl ether (
Aldrich) was transferred individually from ethanol. All initiators are stains
Turned off. As expected, the higher the log P value of the initiator, the less dye damage
It was

[0130]   Example 16   In addition, the characteristics of the radical photoinitiator of the present invention were tested for a number of fragrances as follows.
I tried

By smearing an oily tomato paste (made by Salca; components: sun-dried tomato, sunflower seed oil, white wine vinegar, salt, sugar, flavor, garlic, black pepper and lactic acid) on white cotton cloth, reconstituted in water An oily tomato film was formed. Paste 24
Allowed to dry for hours. This gave a circular stain with a diameter of 4.5 cm. Each fabric was treated with an ethanol solution containing various amounts of perfume. The ethanol was evaporated for 15 minutes. The fabric was irradiated in WOM for 6 minutes to dry. Then wipe the cloth with ECE standard detergent (
Fluorescent material free) at room temperature, 100 rpm for 10 minutes, then rinse,
Tumble dried. (All water was deionized water). Spectraflash
600 was used to measure the fading of stains and the ΔE was measured against the white color of the base fabric.
Measurements were taken at the center and edges of the stain. The average Delta E before treatment was -50 units (at the center of the spot) and 35-40 units (at the edge of the spot).

[0132]   The results are summarized in the table below.

[0133]

[Table 12]

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] August 22, 2001 (2001.8.22)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Contents of correction]

Title: Protective composition for fabric and method for treating fabric

[Claims]

Detailed Description of the Invention

The present invention relates to a fabric protective treatment composition comprising a novel treatment system for stain removal without discoloration. The invention also relates to a method of treating fabrics using a novel treatment system that removes stains without discoloring. The invention further relates to the use of the novel treatment system for stain removal without discoloration, for the protective treatment of fabrics.

BACKGROUND OF THE INVENTION The present invention relates to the treatment of fabrics after the use of the fabric, and in particular to the treatment of the fabric to recover it from the degradation of quality resulting from the use of the fabric, eg stains and stains. Such treatment is hereinafter referred to as cloth protection. Cloth protective treatments include laundry and the use of non-detergent based fabric protective products such as spray products. Ingredients included in fabric protection compositions for the purpose of color fading prevention have received considerable attention. These components include, for example, dye transfer inhibitors, stain removers, photobleaching inhibitors, and fluorescence inhibitors.

European patent application no. 97200107.7 discloses a laundry detergent composition containing a specific polymer system to provide a stain removal effect. International patent application no. PCT / EP97 / 07289 discloses a fabric treatment composition comprising a sunscreen material which prevents fading by sunlight. International patent WO 95/13354
Disclosed is a composition comprising PVPNO as a dye transfer inhibitor and a polymer such as an N-vinylpyrrolidone / N-vinylimidazole copolymer. European patent publication EP
-A-0035470 discloses a fiber treatment composition containing a photobleaching component. The photo-bleaching material has some effect on the spots, but it also acts on the dye.

The inventors of the present invention sought suitable alternative treatment ingredients that could be included in the fabric protective composition for stain removal without discoloration.

The inventors of the present invention have discovered that a radical photoinitiator system that acts by a tie layer stripping mechanism can act as a stain removal component in a fabric protective composition without discoloration.

International Patent WO 96 12785, US Patent US-A-3915974 and Japanese Patent JP 08 239700A each disclose the use of materials having radical initiating properties as perfume ingredients. All of these materials function by a hydrogen abstraction mechanism rather than a tie layer stripping mechanism.

Radical photoinitiators are known per se and are used in fields not relevant to the invention, such as material polymerization reactions, polymer crosslinking reactions and curing reactions.

DEFINITION OF THE INVENTION The present invention thus provides a fabric protection composition comprising a tie-layer strippable radical photoinitiator.

The present invention further provides a method of protective treatment of fabric, which comprises treating the fabric with a tie-peel free radical photoinitiator.

The invention further proposes the use of a tie-layer exfoliated radical photoinitiator in a method of protective treatment of fabrics.

It has been found that the radical photoinitiators of the present invention have the advantage of being stable in solution when stored in the dark. It has been found that these radical photoinitiators do not spontaneously degrade during storage.

Furthermore, it has been found that the radical photoinitiator of the present invention acts on spots without the need for stirring. The advantage obtained by this is that it can be used by a simple coating method. Further, damage to the cloth such as fibrillation (defibration) can be prevented.

It has been found that the radical photoinitiator system of the present invention is soluble or dispersible in media other than water and can be used in apparel limited to dry cleaning.

Finally, it has been found that the radical photoinitiators of the invention have a bactericidal effect.

[0015]     (Detailed explanation)   Radical photoinitiator   Suitable radical photoinitiators that can be used in the present invention will stain fabric when photoexcited.
It is a component that produces radicals that can attack.

[0016]   The tie-layer exfoliated radical photoinitiator has the following reactions:

[0017]

[Chemical 1] [Wherein k (2) represents the rate constant of the bonding layer peeling reaction]. Preferably k (2) is greater than 10 ⁶ s ^-1 .

Suitable tie layer stripping free radical initiators may be selected from the following group: (A) Alpha amino ketones, especially alpha amino ketones containing a benzoyl moiety, which is also referred to by another name as alpha-aminoacetophenone, eg 2-methyl-1-
[4-phenyl] -2-morpholinopropan-1-one (trademark Irgacure
907), (2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trademark Irgacure 369). (B) Alpha hydroxyketones, especially alpha-hydroxy-acetophenone, e.g. 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one) (Trademark Irgacure 295
9), 1-Hydroxy-cyclohexyl-phenyl-ketone (trademark Irgacu
re 184). (C) Phosphorus-containing photoinitiators such as monoacyl and bisacylphosphine oxides and sulfides, eg 2-4-6- (trimethylbenzoyl) diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl- Phosphine oxide (Trademark Irgacure 819). (D) Dialkoxy acetophenone. (E) Alpha-haloacetophenone. (F) Trisacylphosphine oxide.

Suitable radical photoinitiators are international patent WO9607662 (Trisacylphosphine oxide), US patent US5399782 (phosphine sulfide), US
541060, European Patent Publications EP-A-57474, EP-A-73413 (
Phosphine oxide), EP-A-0888050, EP-A-0117233,
EP-A-0138754, EP-A-0446175 and US patent US455.
9371.

Suitable photoinitiators are, for example, European Patent Publication EP-A in the name of Ciba Geigy.
-0003002, EP-A-0446175 in the name of Ciba Geigy, C
British patent GB2259704 (alkyl bisacylphosphine oxide) in the name of iba Geigy, US Pat. No. 4,792,632 (bisacylphosphine oxide), US Pat. Is disclosed in.

The radical photoinitiator is based on A. F. Cunningham, V.I. Desorby,
K. Dietliker, R .; Husler and D.H. G. Leppard
, Chemia 48 (1994) 423-426.

Without wishing to be bound by theory, it is preferred that all radical photoinitiators react via the excited triplet state to reduce the effects of the cage effect.

Radical photoinitiators suitably undergo one of the reactions presented above when excited by radiation, generally in the range 290-800 nm. For example, natural sunlight, including light in this region, will adequately cause one of the reactions described above for radical photoinitiators. Preferably, the radical photoinitiator is in the ultraviolet range (290-400 nm
) Has a maximum extinction coefficient of greater than 100 mol ⁻¹ 1 cm ⁻¹ . Suitably the radical photoinitiator is solid or liquid at room temperature.

Suitably the radical photoinitiator is substantially colorless and a colorless photoproduct is obtained when one of the reactions presented above occurs.

Preferably the composition is for example European Patent Publication EP-A-0088050, EP-
Sensitizers such as thioxanthone described in A-0138754.

[0026]   Preferred radical photoinitiator system   The inventors of the present invention have a certain hydrophobicity as measured by the log P value.
It has been found that the radical photoinitiators that are used have particularly favorable effects. Remove stains
All materials intended to be used also have the property of attacking dyes. Preferred
The radical photoinitiator system has an excellent balance of stain removal effect and dye aggressiveness.
ing.

Preferably the radical photoinitiator has a high log P value. Here lo
g P is the octanol-water partition coefficient. It is preferred that the radical photoinitiator has a log P measured at 25 ° C. of greater than 2.5, more preferably greater than 4.0.

[0028]   Cloth protection composition   The present invention relates to an industrial or household cloth laundry composition and a cloth conditioning composition.
And a cloth washing and conditioning composition (so-called detergent-introducing type (thro
Suitable for use in a ugh the wash) conditioner composition)
It The present invention also relates to non-detergent based fabric protection compositions for industrial or domestic use, such as
, Can be used in spray compositions.

[0029]   Cloth laundry composition   The fabric laundry composition according to the present invention may be in any suitable form, eg powder form, compression molding.
It may be in the form of a powder detergent, a liquid detergent or a solid bar detergent.

The laundry laundry composition of the present invention is a laundry laundry selected from non-soap anionic surfactants, nonionic surfactants, soaps, amphoteric surfactants, zwitterionic surfactants and mixtures thereof. Including detergent material.

Suitable anionic surfactants are known to those skilled in the art and include alkylbenzene sulfonates, primary and secondary alkyl sulphates, especially C8-C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyls. There are xylene sulfonates, dialkyl sulfosuccinates; ether carboxylates; isethionates; sarcosinates; fatty acid ester sulfonates and mixtures thereof. Sodium salts are generally preferred.

Nonionic surfactants are also known to those skilled in the art, and are primary and secondary alcohol ethoxylates, especially C ₈ -C ₂₀ fats ethoxylated with an average of 1-20 moles of ethylene oxide per mole of alcohol. family alcohols, more particularly aliphatic primary and secondary alcohols of C _{1 0} -C ₁₅ ethoxylated with an average 1-10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamides). Mixtures of nonionic surfactants may be used.

Suitable detergent compositions that may be used in household or industrial fully automatic cloth washing machines are generally anionic non-soap surfactants or nonionic surfactants, or as known to those skilled in the art. A suitable mixture of both surfactants in appropriate proportions, optionally with soap.

Many suitable detergent-active compounds are available, eg “Surface-A”.
ctive Agents and Detergents ", Volumes
I and II, Schwartz, Perry & Berch.

The anionic surfactant is suitably 5 wt% -50 based on the fabric treatment composition.
It is present at a level of weight%, preferably 10-40% by weight. The nonionic surfactant is suitably present at a level of 1-20% by weight, preferably 5-15% by weight.

The total amount of surfactant present depends on the intended end use, and may be present in as much as 60% by weight in the fabric hand wash composition. Amounts of 5-40% by weight are generally adequate in machine-washing fabric compositions.

[0037]   Detergency builder   The detergent compositions of the present invention generally further contain one or more detergency builders.
Will. The total amount of detergency builder in the composition is 5-80% by weight, preferably 10
-60% by weight may be suitable.

Inorganic builders that may be present include British Patent GB 1,437,950 (Uni
sodium carbonate, if desired in combination with calcium carbonate crystallization seeds as disclosed in Lever); crystalline and amorphous aluminosilicates, eg
Zeolites as disclosed in GB 1,473,202 (Henkel) and crystalline / amorphous aluminosilicate mixtures as disclosed in GB 1,470,250 (Procter &Gamble); European Patent EP16451.
There are layered silicates such as those disclosed in 4B (Hoechst). Inorganic phosphate builders such as sodium orthophosphate, sodium pyrophosphate and sodium tripolyphosphate may also be suitably used in the present invention.

The detergent composition of the present invention preferably contains an aluminosilicate of an alkali metal, preferably sodium, as a builder. Sodium aluminosilicate is generally included (on an anhydrous basis) in an amount of 10-70% by weight, preferably 25-50% by weight.

[0040]   Alkali metal aluminosilicates can be crystalline, amorphous or a mixture of both.
General formula:       0.8-1.5Na_TwoO. Al_TwoO_Three． 0.8-6 SiO_Two Can have

These materials contain some bound water and contain at least 50 mg C
It is required to have a calcium ion exchange capacity of aO / g. Preferred sodium aluminosilicates contain (in the above formula) 1.5-3.5 SiO2 units. Both amorphous and crystalline materials can be readily prepared by the reaction of sodium silicate and sodium aluminate. This reaction is well documented in the literature.

A suitable ion-exchange detergency builder consisting of crystalline sodium aluminosilicate is, for example, British Patent GB 1,429,143 (Procter & Gamble.
)It is described in. Preferred sodium aluminosilicates of this type are the commercially available known zeolites A and X, and mixtures thereof.

The zeolite may be the commercially available zeolite 4A, which is currently widely used in laundry powder detergents. The zeolite builder contained in the composition of the present invention is European Patent EP38.
It may be Maximum Aluminum Zeolite P (Zeolite MAP) as described and claimed in 4070A (Univer). Zeolite MAP is 1.
33 or less, preferably in the range of 0.90 to 1.33, more preferably 0.90-
It is defined as a zeolite P type alkali metal aluminosilicate having a silicon to aluminum ratio in the range of 1.20.

Zeolites MAP having a silicon to aluminum ratio of 1.07 or less, more preferably about 1.00 are particularly preferred. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO / g anhydrous material.

Organic builders which may be present include polyacrylates, polycarboxylate polymers such as acrylic / maleic copolymers and acrylic phosphinates; citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxys. Polycarboxylate monomers such as methyloxysuccinate, carboxymethyloxymalonate, dipicolinate, hydroxyethyliminodiacetate, alkyl- and alkenylmalonates and succinates; and sulfonated fatty acid salts. This list is not an exhaustive list of organic builders.

Particularly preferred organic builders are 5-30% by weight, preferably 10-25% by weight.
Citrate used in a suitable amount of 0.5-15% by weight, preferably 1-10% by weight of an acrylic polymer, more particularly an acrylic / maleic copolymer.

Both inorganic and organic builders are preferably present in the form of alkali metal salts, especially sodium salts.

[0048]   Bleaching ingredients   The detergent composition of the present invention also provides a peroxy bleach that can generate hydrogen peroxide in aqueous solution.
Whitening systems, such as inorganic persalts or organic peroxy acids, may optionally be included.

Suitable peroxy bleach compounds include organic peroxides such as urea peroxide,
And inorganic persalts such as alkali metal perborate, percarbonate, perphosphate,
There are persilicates and persulfates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate and sodium percarbonate.

Particularly preferred is sodium percarbonate which has a protective coating which prevents destabilization due to humidity. Sodium percarbonate with a protective coating consisting of sodium metaborate and sodium silicate is disclosed in British Patent GB 2,123,044B (Kao).

The composition may further contain a photobleaching system, for example as described in EP-A-0035470.

[0052]   Fabric softening composition   The fabric treatment composition of the present invention may be a fabric conditioning composition or a fabric conditioner.
It may also include a positioner.

[0053]   Cloth softener compound   The fabric softener compound is preferably a cationic, nonionic or anionic fabric softener.
It is a softener compound.

The fabric softener compound may be a quaternary ammonium material containing a polar head group and one or two alkyl or alkenyl chains. The fabric softener compound may also be a non-ionic fabric softener compound such as a fabric softening oil, or a fabric softening silicone composition or a fabric softening ester composition such as a sugar ester.

Particularly preferably, the fabric softener compound has two long chain alkyl or alkenyl groups having an average chain length longer than C ₁₄ , more preferably each chain is longer than C _14. It has an average chain length, more preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of C ₁₈ .

It is preferred that the long chain alkyl or alkenyl groups of the fabric softener compound are predominantly linear.

It is highly preferred that the fabric softener compound is substantially water insoluble. A fabric softener compound that is substantially insoluble in the context of the present invention is a fabric softener compound having a solubility of less than 1 × 10 ⁻³ wt% in deionized water at 20 ° C., preferably less than 1 × 10 ⁻⁴ wt%. A fabric softener compound having a solubility of 1, most preferably 1 in deionized water at 20 ° C.
It is defined as a fabric softener compound having a solubility of ^{x10 -3} -1 x 10 ^-6 .

[0058]   formula:

[0059]

[Chemical 2] [Wherein R ¹ and R ² represent a hydrocarbyl group having 12 to 24 carbon atoms, R ³ and R ⁴ represent a hydrocarbyl group containing 1 to ⁴ carbon atoms, and X is an anion, preferably Representing an anion selected from a halogen group, a methylsulfate group and an ethylsulfate group], quaternary ammonium compounds of the known type which are substantially water-insoluble and are preferred.

Representative examples of these quaternary softeners are di (tallowalkyl) dimethylammonium methylsulfate, dihexadecyldimethylammonium chloride, di (hydrogenated tallowalkyl) dimethylammonium chloride, dioctadecyldimethylammonium chloride, Di (hydrogenated tallow alkyl) dimethylammonium sulfate, dihexadecyldiethylammonium chloride, di (coco palm alkyl) dimethylammonium chloride, ditallowalkyldimethylammonium chloride and di (hydrogenated tallowalkyl) dimethylammonium chloride (
Trademark Arquad 2HT).

Another preferred softener contains ester or amide bonds, eg Ac
It is available under trademarks such as soft 580, Varisoft 222 and Stepantex.

A particularly preferred fabric softener compound is a water insoluble quaternary ammonium material consisting of a compound having two C _12-18 alkyl or alkenyl groups attached to the molecule through at least one ester bond. is there. More preferably, the quaternary ammonium material has two ester bonds. Preferred ester linked quaternary ammonium materials that can be used in the present invention have the formula:

[0063]

[Chemical 3] Wherein each R ¹ group is independently a C _1-4 alkyl group, a hydroxyalkyl group or a C 2 -group.
4 alkenyl groups, each R ² group is independently selected from a C 8 _-28 alkyl or alkenyl group, and T is

[0064]

[Chemical 4] , X ⁻ represents an appropriate arbitrary anion, and n represents an integer of 0-5. Di (ethyl ester) dimethyl ammonium chloride (DEEDMAC) is particularly preferred.

[0065]   A second preferred type of quaternary ammonium material has the formula:

[0066]

[Chemical 5] [Wherein R ₁ , n, X ⁻ and R ₂ have the same meanings as defined above].

[0067]   It is advantageous for environmental reasons if the quaternary ammonium material is biodegradable.

Preferred materials of this class such as 1,2-bis [cured tallowyloxy] -3-trimethylammonium propane chloride and their method of preparation are described, for example, in US Pat. No. 4,137,180 (Lever Brothers). ing. Preferably these materials contain minor amounts of the corresponding monoesters such as those described in US Pat. No. 4,137,180, eg 1-cured tallowyloxy-2-hydroxytrimethylammonium propane chloride.

The fabric softeners can also be quaternary polyol esters, such as those described in European Patent EP 0 638 639 (Akzo).
PEQ).

[0070]   Other ingredients   The composition of the present invention also comprises a pH buffering agent, a perfume carrier, a fluorogenic agent, a coloring agent, a hydrous agent.
Tropes, foam suppressors, anti-settling agents, enzymes, optical brighteners, opacifiers, shrink-proofing agents, wrinkle-preventing agents
Agents, anti-spot agents, bactericides, fungicides, preservatives, drape imparting agents, antistatic agents and
And one or more optional ingredients selected from ironing aids.

The present invention may be in the form of a dilute or concentrated aqueous solution or suspension, for example as described in WO 97/15651, WO 95/27769. Alternatively, the fabric softening composition may be in the form of a powder that can be used in the rinse cycle of a fully automatic washing machine. Alternatively, the fabric softening composition may be, for example, International Patent WO95 / 2777.
It may also be in the form of a sheet of a fabric conditioning composition that can be used in a tumble dryer, as disclosed in No. 7. Alternatively, the fabric conditioning composition may be in the form of a substantially non-aqueous concentrate as described in International Patent Application PCT / EP99 / 00497.

The laundry detergent composition according to the present invention may further comprise a detergent-type softener, such as a cationic fabric softener.

[0073]   Non-detergent based cloth protection products   The present invention can also be used in non-detergent based fabric protection products. For example, if the product is
A void system may be included as a main component. For example, a non-detergent-based composition may
Consists of a stain remover solution in a suitable solvent such as propanol, alcohol, etc.
Good. The composition may be an aerosol composition or a spray composition. The composition is
Stick-shaped, stick-shaped, or pressure applied to the surface by absorbing with a sponge
It may be in the form of a coating composition.

[0074]   The invention will be explained in more detail on the basis of the following non-limiting examples.

[0075]   Example   Unless otherwise specified, all amounts are percent by weight or parts by weight.

The following radical initiators are used in these examples. These are Ciba S
It is commercially available under the tradenames below from specialty Chemicals.

Irgacure 369-1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (log P
= 2.9, measured at 25 ° C).

Irgacure 819-bis (2,4,6-trimethylbenzoyl)
-Phenylphosphine oxide (log P = 5.8, measured at 25 ° C).

Irgacure 2959- (1- [4- (2-hydroxyethoxy)
-Phenyl] -2-hydroxy-2-methyl-1-propan-1-one (log
P = 0.84, measured at 25 ° C.).

[0080]   Example 1   Cloths with the types of stains listed in Table 1 were obtained from a supplier (Equest
, Aged for 3 days and then sealed). Next, a variety of stain cloths
With a solution of ethanol containing a radical photoinitiator of
Place in S3000 Weatherometer WOM ™ for 12 minutes
I had (0.35w / m^TwoAt a power level of 340 nm). Spectra
The reflectance at 460 nm (measured using a flash SF60 ™ reflectometer (
The change in R (460 nm)) is shown in Table 4.

The following treatment scheme was used: Treatment 1-no dipping Treatment 2-Stained cloth is placed in ethanol, removed, dried, moistened with water and placed in a Weatherometer for 12 minutes.

Treatment 3--Place in ethanol containing 0.20 wt% Irgacure 2959 ™, remove, dry, moisten with water, place in WOM and hold for 12 minutes.

Treatment 4-Put in 0.20% by weight of Irgacure 819 ™ in ethanol, remove, dry, moisten with water and place in a Weatherometer for 12 minutes.

[0084]   The results are shown in Table 1.

[0085]

[Table 1]

Radical initiators generally increase the reflectance of various stains at 460 nm. That is, the radical initiator effectively removes stains from the cloth.

[0087]   Example 2   Except for varying the amount of Irgacure 819 ™ in ethanol.
The procedure of Example 1 was repeated using Reasons 1, 2 and 4. The results are shown in Table 2.

[0088]

[Table 2]

The results show that stains are eliminated by very low levels of radical photoinitiator based on the weight of the fabric.

[0090]   Example 3   To compare the effect of various radical initiator systems on stains and dyes, the following
An experiment was conducted. I bought a cotton cloth with various kinds of stains from the above-mentioned Equest
It was Various on the basis of cloth weight (on-weight-fabric, owf)
From ethanol to a spotted cloth by slamming a level of photoinitiator
Transferred. The ethanol was then evaporated, the cloth dampened with deionized water and Atla
Place in S3000 Weatherometer ™ and illuminate for 12 minutes
(Power = 0.35W / m^TwoIrradiation to 340 nm). Cloth with stains and 1
The reflectance of the stain-free cloth piece was measured at 460 nm, and the ΔE value was calculated. these
Values were compared to controls. The control was that the ethanol contained no radical initiator.
Except for and, the stains are treated in the same way. As in Example 1, the initiator was
Excellent stain-eliminating effect on curry, bolognese, β-carotene and chilli
It was found to have. Tables 3 and 4 show various levels based on the weight of the fabric.
Of Irgacure 2959 and 819.TM.
It is shown that the average decrease in ΔE of various stains was above the control.

To determine how much the initiator damages the dye, the above experiment was repeated using a print cloth purchased from Veebee The of Harrogate England, instead of the spotted cloth. In this case, the ΔE value represents dye damage. Sixteen different dyes were tested and the average dye damage measurements are shown in Tables 3 and 4.

[0092]   The following dyes were used.

[0093]

[Table 3]

Dividing the stain removal measurement by the dye damage measurement gives the benefit / harm value.
This value represents how specific the initiator is for stains over the dye. Two
． Irgacure 819 ™, which has a log P of greater than 5, is 2.
It will be appreciated that it is much more highly spot-specific than Irgacure 2959 ™, which has a log P below 5. This is a low level (0-0
． 02% owf), and at this level Irgacure 819 (
Trademark) provides a strong stain removal effect, but very little dye damage.

[0095]

[Table 4]

[0096]

[Table 5]

Note that a much lower degree of dye damage was observed when the experiment was repeated using a dry cloth. However, the spot erasing effect also decreased.

[0098]   Examples 4 and 5   The following base powders were prepared:   Linear alkylbenzene sulfonate sodium (LAS) 23.60%   Sodium tripolyphosphate-19.22%   Sodium silicate-4.81%   Sodium sulfate-28.59%   Calcite (calcium carbonate) -10.30%   Trace component-1.08%   Water-12.49%

In Example 4, 1 gram of this base powder was added to 0.024 g of Irgacure.
Intimately mixed with 819. The final product is 2.3% by weight of Irgacure 819.
Contains. In Example 5, 1 gram of this base powder was added to 0.024 g of I.
Intimately mixed with rgacure 369. The final product is 2.3 wt% Irgac
It contains ure 369.

In each example, the mixture of base powder and radical photoinitiator was dissolved in 400 grams of water at 40 ° C. Three cotton cloth lots were prepared. Each lot contained a total weight of 16.1 grams of soft cotton and a total weight of 10 grams of brushed cotton. The cotton cloth was all white. For each lot, both types of cloth were cut into four pieces.
The lot was then washed for 5 minutes with the solution prepared above. A piece of soft cotton and a piece of brushed cotton were taken out and dried. The wash was discarded and the cotton cloth was rinsed with 600 grams of cold water. A piece of soft cotton and brushed cotton was taken out and dried. The first rinse was then discarded. A second rinse was then done with another 600 grams of water. A piece of soft cotton and a piece of brushed cotton were removed again.

In order to know the amount of the initiator adhering to the cloth, the strips of soft cotton and brushed cotton taken at each stage were tested. This measurement was performed by measuring the reflectance of the dry cloth at 320 nm using a Spectraflash SF60 ™ reflectance spectrometer. The following results were obtained.

[0102]

[Table 6]

[0103]

[Table 7]

In all cases, the reflectance of the fabric washed with the powder composition containing the radical initiator is lower than the reflectance of the fabric washed with the control composition without the radical initiator. The reason is that the Irgacure radical initiator is strongly absorbed at 320 nm and reduces the reflectance. The measured reflectance change is significantly above the noise level of this type of measurement, demonstrating the attachment of the initiator.

Examples 4 and 5 demonstrate that radical photoinitiators can adhere to fabrics from laundry compositions.

[0106]   Example 6   The following rinse conditioner formulations were prepared:   HEQ¹  -4%   Fragrance-0.3%   Irgacure 819 ™ -0.66%   Water-up to 100%   1 HEQ = 1,2 bis [cured tallowyloxy] -3-trimethylan
Monium propane chloride, manufactured by Hoechst.

3 grams of this rinse conditioner was dissolved in 600 grams of cold water. 1
8 grams of cotton cloth was placed in this solution and held for 5 minutes. After this time, the cotton cloth was taken out and dried. The reflectance spectrum of the plain cotton was measured at 320 nm using a Spectraflash SF60 ™ reflectometer.

Approximately 0.003% (based on fabric weight) of radical photoinitiator was provided, calculated from the reflectance results.

[0109]   Example 8   The following experiment is to test the effect of pH on the effect of radical photoinitiator.
went.

The procedure of Example 7 was repeated except that the ethanol was transferred to the spotted cloth by beating 0.1% Irgacure 819 ™ based on the weight of the cloth. Independent samples were taken for each stain and moistened with buffer solutions of different pH. The resulting fabric is Atlas S3000 ™ Weather.
It was put in an ometer and irradiated for 12 minutes. The change in average reflectance at 460 nm after the treatment is shown in the table. The average reflectance at 460 nm for the four treatments was 46.5. It will be appreciated that radical photoinitiators provide a substantial improvement in reflectance over a wide pH range.

[0111]

[Table 8]

[0112]   Example 9   Lucerin TPO-L (2,4) at 0.02 and 0.2% owf respectively
, 6-Trimethylbenzoylethoxyphenylphosphine oxide, manufactured by BASF
) And Irgacure 184 (1-hydroxy-cyclohexyl-phenyl
The experiment of Example 3 was repeated using-(ketone, Ciba). The result is
It shows in Table 8.

[0113]

[Table 9]

[0114]   Example 10   A white polyester cloth with stains (Veebee Tech) is used as a preceding example.
When treated with the same initiator as above, a superior cleaning effect over the control was observed. Dyeing
Little damage was observed with the colored polyester cloth.

[0115]   Example 11   Tomato paste (Traditional Ragu Recip) on Tenjiku cotton
e Van den Bergh foods, ingredients: tomato, sunflower oil, ta
Onions, salt, sugar, glucose, garlic powder, basil, parsley, spice extract
, Citric acid, basil, parsley, CaCl_Two) And aging in air for 1 day
The oily tomato stain was attached by doing. Linen the cloth with stains
And washed under the following conditions. 12g of cloth in each tank (6g of which is
Cloth), 240ml water, 0.34g borax, 1.44g liquid detergent
And washed at a temperature of 40 ° C. for 20 minutes and not rinsed. Tumble dryer
And dried in WOM and held for 6 minutes.

The liquid detergent is Coco 5EO (Clariant-nonionic surfactant), S
DS (sodium dodecyl sulfate-anionic surfactant), CTAC (cetyltrimethylammonium chloride-cationic surfactant), Arquad 2H
Prepared from T (Akzo Nobel-Cationic Surfactant), 0.1% Lucerin TPO-L, 10% ethanol, and a balance amount of water, based on the weight of the formulation. The amount of surfactant in each formulation is shown in the table.

[0117]

[Table 10]

The results are shown below. In all cases, the samples containing the initiator showed lower ΔE values than the control (better stain removal effect than the control).

[0119]

[Table 11]

[0120]   Example 12   Formulation of Example 11 using Irgacure 819 instead of TPO-L
The thing L1 was prepared. Excellent stain removal effect over the control was obtained.

[0121]   Example 13   15.3% anionic surfactant, 10% ethanol, 0.1% Luc
A detergent composition was prepared containing erin TPO-L and a balanced amount of water.
The anionic surfactants were LAS and SDS.

When these were tested in the wash protocol of Example 11, both showed a significant increase in the stain removal effect after irradiation compared to the water alone control. This indicates that the initiator in the wash was effective. Beneficial results were also observed with β-carotene and paprika stains.

[0123]   Example 14   Persil solution was purchased at Ireland and the product contained 0.01% by weight of Luce.
rin TPO-L was added. wash and rinse the β-carotene stain cloth
Upon irradiation, the stain removal effect was found to be much greater in the presence of the initiator.
Was done.

[0124]   Example 15   On a cotton cloth stained with β-carotene, an initiator, benzoin, dimethoxypheny
Luacetophenone, benzoin methyl ether and benzoin ethyl ether (
Aldrich) was transferred individually from ethanol. All initiators are stains
Turned off. As expected, the higher the log P value of the initiator, the less dye damage
It was

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 7/34 C11D 7/34 7/36 7/36 7/54 7/54 D06L 1/12 D06L 1 / 12 D06M 13/127 D06M 13/127 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT , SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN , IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor Coleman, Collet Elizabeth UK, Merseyside H.63.33 J.A.Dabrill, Weihallal, Bebington, Quarry Road East, Unilever Research Port Sunlight (72) Inventor Cloffaud, Robert. The United Kingdom, Merseyside H.63.3, J.A.Dabrilleu, Weihallal, Bevington, Quarry Road East, Unilever Research Port Sunlight (72) Inventor Fairkraf, Linett United Kingdom , Merseyside H.63.3, J.A.Dabrilleu, Wiaral, Bebington, Quarry Road East, Unilever Research Port Sunlight F-Term (reference) 4H003 AB19 DA01 DA03 EA09 EA12 EA15 EA16 EB03 EB21 EB23 ED02 EE11 FA08 FA22 FA42 4L033 AB04 AB05 AB06 AC15 BA09 BA36 BA46

Claims (13)

[Claims] 1. A fabric protective composition comprising a radical photoinitiator selected from hydrogen abstraction type photoinitiators, tie layer exfoliation type radical photoinitiators and mixtures thereof. 2. The composition of claim 1 which is a fabric conditioner composition further comprising a fabric conditioner. 3. The composition according to claim 2, which is a rinse conditioner. 4. The composition according to claim 1, which is a fabric cleaning composition further containing a laundry detergent. 5. Composition according to claim 4, characterized in that the laundry detergent is selected from non-soap anionic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof. 6. The composition according to claim 4, further comprising a builder material. 7. The radical photoinitiator is a hydrogen abstraction radical photoinitiator selected from the group consisting of benzophenone, acetophenone, pyrazine, quinone, benzyl and mixtures thereof. The composition according to any one of 1. 8. The radical photoinitiator is an alpha aminoketone, preferably alpha-aminoacetophenone, alpha-hydroxyketone, preferably alpha-hydroxyacetophenone, monoacyl and bisacylphosphine oxides and sulfides, dialkoxyacetophenone, alpha haloacetylphenone,
7. Composition according to any one of claims 1 to 6, characterized in that it is selected from the group consisting of trisacylphosphine oxide and mixtures thereof. 9. The composition according to claim 1, wherein the radical photoinitiator is excited by light substantially in the range of 296-460 nm. 10. A method of protective treatment of a fabric comprising treating the fabric with a radical photoinitiator selected from hydrogen abstraction type radical photoinitiators, tie layer exfoliation type radical photoinitiators and mixtures thereof. 11. The method according to claim 10, wherein the treatment of the fabric is carried out during the washing stage of the fabric. 12. The method according to claim 10, wherein the treatment is carried out in the presence of a fabric conditioner during the rinsing step of the fabric. 13. Use of a radical photoinitiator selected from a hydrogen abstraction type radical photoinitiator, a tie layer exfoliation type radical photoinitiator and a mixture thereof in a method for protective treatment of cloth.