Processing of cloth

[0001] The present invention is used to improve the sun protection rate (SPF) of a fabric treatment composition, particularly a composition containing a fluorescent whitening agent, and a textile fiber material treated with the composition. It relates to a method of processing a cloth using an object.

[0002] It is known that light rays having a wavelength of 280 to 400 nm cause tanning of the epidermis. It is also known that light rays with a wavelength of 280 to 320 nm (called UV-B radiation) cause erythema and skin burning, which can suppress browning of the skin. Radiation with a wavelength of 320-400 nm (called UV-A radiation) induces browning of the skin, but can also cause skin damage, especially for sensitive skin exposed to long-term sunlight. Are known. Examples of such disorders include loss of skin elasticity, development of wrinkles, accelerated initiation of erythematous reactions, induction of phototoxic or photoallergic reactions. Means of effective protection of the skin from damage due to overexposure to sunlight need to include means of absorbing both UV-A and UV-B components of sunlight before they reach the skin surface. it is obvious.

[0003] Conventionally, in order to protect human skin exposed from potential damage caused by UV components in sunlight, a preparation containing a UV absorber has been directly applied to the skin. Awareness of the potential dangers of overexposure to sunlight has increased significantly, especially in areas where the sun is shining, such as Australia and the United States, circulated by fear of the consequences of ozone depletion. ing. Some of the most disastrous examples of skin disorders caused by overexposure to unprotected sunlight are the development of melanoma or carcinoma of the skin.

[0004] One aspect of the demand for increased levels of skin protection against sunlight was to consider additional measures to be taken in the face of direct skin protection. For example, clothing was considered to protect the skin from direct exposure to sunlight. Most natural and synthetic fiber materials are at least partially permeable to the UV components of sunlight. Therefore, simply wearing clothing does not adequately protect the underlying skin from UV radiation damage. Clothing with dark dyes and / or finely woven fabrics can provide some protection to the underlying skin, but from the standpoint of the wearer's personal comfort, the above clothing is sunny. Not practical in rural areas.

[0005] Therefore, it is necessary to protect the skin under the garment from UV light, including lightweight summer garments that are undyed or dyed very lightly. Depending on the type of dye, UV protection may be required even on skin covered with slightly darker clothing. Such lightweight summer clothing is usually 200g / m²It has a density of less than 1.5 to 20 sun protection, depending on the type of fiber used to make the garment. The SPF rating of a sunscreen (sunscreen cream or clothing) can be defined as a multiple of the time it takes for the average person wearing sunscreen to develop sunburn under average sun exposure conditions. For example, if the average person develops sunburn after 30 minutes under standard exposure conditions, sunscreens with an SPF rating of 5 can extend the protection time from 30 minutes to 2 hours and 30 minutes. For people with average fair skin during the hottest hours of the day, for light clothing, the average tan time is minimal, for example only 15 minutes, especially for people living in sunny areas. Is preferably at least 20 SPF grades.

[0006] Surprisingly, it is compatible with fabric care ingrudient.<u style="single">(Compatibility)</u>There are fluorescent whitening agents, preferably cation, amphoteric, or anionic fluorescent whitening agents, which are phased with rinse cycle fabric care formulations, especially fabric softener components.<u style="single">Yong</u>Rinse cycle fabric softeners containing higher amounts of optical brighteners, preferably cationic, amphoteric, or anionic optical brighteners than used in conventional rinse cycle fabric protective formulations. It has been found that when applied to washed articles, the fibrous materials treated in this way provide excellent whiteness and sun protection.

[0007] Therefore, as a first feature, the present invention is in phase with the cloth protective component.<u style="single">Yong</u>A cloth protective ingredient, preferably a cationic, amphoteric, or anionic optical brightener, preferably 0.3 to 10% by weight, preferably 0.3 to 3% by weight, based on the total weight of the composition. Provided is a stable and concentrated cloth rinsing composition comprising a cloth softener, a stain removing component or a stain preventing component, or a waterproofing agent, the balance being substantially water. The cloth protective component is present in an amount of 2 to 25% by weight, preferably 5 to 20% by weight, based on the total weight of the composition.

[0008] As a second feature, the present invention contains a cloth protective component, preferably a cationic cloth softener, in an amount of 2 to 25% by weight, preferably 5 to 20% by weight, which is compatible with the cloth protective component.<u style="single">Yong</u>Stable and concentrated containing 0.3-10% by weight, preferably 0.3-3% by weight, of fluorescent optical brighteners, preferably cations, amphoteric or anionic optical brighteners, the balance being substantially water. Rinse cycle cloth softener composition is provided.

[0009] Preferred examples of cationic fabric softeners are imidazolines, quaternary ammonium compounds, esteramide amine salts, and mixtures thereof. A preferred imidazoline cationic fabric softener has the following formula.

[Chemical 20]<img file="JP4046366B2_D0001.tif" />In the formula, R is hydrogen or C₁-C₄Alkyl and R₁Is C₈-C₃₀Aliphatic residue, R₂Is -C₂H₄-O (C = O) -R₁Or -C₂H₄-NH (C = O) -R₁And A^-Is an anion. Preferably R is hydrogen or methyl and R₁Is C₁₄-C₁₈Alkyl or C₁₄-C₁₈Alkenyl and R₂Is -C₂H₄-O (C = O) -C₁₄-C₁₈Alkyl or -C₂H₄-O (C = O) -C₁₄-C₁₈Alkenyl, or -C₂H₄-NH (C = O) -C₁₄-C₁₈Alkyl, or -C₂H₄-NH (C = O) -C₁₄-C₁₈It is alkenyl.

[0010] Other preferred imidazoline cationic fabric softeners have the following formula.

[Chemical 21]<img file="JP4046366B2_D0002.tif" />In the formula, R₁And A^-Has the above meaning, R₃And R₄Independent of C₈-C₃₀Aliphatic residue, C₁-C₄Alkyl, C₁-C₄Halogenoalkyl, C₁-C₄Hydroxyalkyl, or -C₂H₄-N (R)₅) -C (= O) -R₆(Here R₅Is hydrogen or C₈-C₃₀Alkyl and R₆Is hydrogen or C₁-C₄It is alkyl). Preferably R₁Is C₁₄-C₁₈Alkyl or C₁₄-C₁₈Alkenyl and R₃Is C₁₄-C₁₈Alkyl, C₁₄-C₁₈Alkenyl, C₁-C₄Alkyl, C₁-C₄Halogenoalkyl, or C₁-C₄Hydroxyalkyl, R₄Is -C₂H₄-N (R)₅) -C (= O) -R₆(Here R₅Is hydrogen or C₈-C₃₀Alkyl and R₆Is hydrogen or C₁-C₄It is alkyl). Preferred anion A^-Chloride, bromide, iodide, fluoride, sulfate, metosulfate, nitrite, nitrate, or phosphate anion, and acetate, adipate, phthalate, benzoate, stear Includes acid salts, or carboxylate anions such as oleate anions.

[0011] Examples of preferable special compounds of the formula (1) include the following. 2-Tallow 1-2 (2-stearoyloxyethyl) -imidazolin chloride, 2-tallow-1- (2-stearoyloxyethyl) -imidazoline sulfate, 2-tallow-1- (2-stearoyloxyethyl) -imidazoline Methosulfate, 2-Tallow -1-Methyl-3- (2-Stearoylamide Ethyl)-Imidazolinkolide, 2-Tallow -1-Methyl-3- (2-Stearoylamide Ethyl)-Imidazoline Sulfate, 2-Tallow -1-Methyl-3- (2-stearoylamide ethyl) -imidazoline metosulfate.

[0012] Special examples of the preferred compound of formula (2) include: 2-Heptadecyl-1-methyl-1-oleylamide ethyl-imidazolinium metosulfate, 2-heptadecyl-1-methyl-1- (2-stearoylamide) ethyl-imidazolinium metosulfate, 2-heptadecyl- 1-Methyl-1- (2-stearoylamide) ethyl-imidazolinium chloride, 2-coco-1- (2-hydroxyethyl) -1-benzyl-imidazolinium chloride, 2-coco-1- (2-coco-1- (2-) Hydroxyethyl) -1- (4-chlorobutyl) -imidazolinium chloride, 2-coco-1- (2-hydroxyethyl) -1-octadecenyl-imidazolinium chloride, 2-wallow-1- (2-hydroxyethyl) ) -1-Benzyl-imidazolinium chloride, 2-wallow -1- (2-hydroxyethyl) -1- (4-chlorobutyl) -imidazolinium chloride, 2-heptadecenyl-1- (2-hydroxyethyl)- 1- (4-Chlorobutyl) -imidazolinium chloride, 2-heptadecenyl-1- (2-hydroxyethyl) -1-benzyl-imidazolinium chloride, 2-heptadecenyl-1- (2-hydroxyethyl) -1- Octadecil-Imidazolinium chloride.

[0013] One class of preferred quaternary ammonium compounds has the following formula.

[Chemical 22]<img file="JP4046366B2_D0003.tif" />In the formula, R₇Is C₈-C₃₀Aliphatic residue, R₈, R₉, R₁₀, R₁₁And R₁₂Is independently hydrogen, C₁-C₄Alkyl, or C₁-C₄Hydroxyalkyl, A^-Has the above meaning, m is an integer of 1 to 5, and n is an integer of 2 to 6. The preferred compound of formula (3) is R₇Is C₁₂-C₁₈Alkyl and R₈, R₉, R₁₀, R₁₁And R₁₂Is independently C₁-C₄Alkyl, especially methyl compounds.

[0014] Special examples of the preferred compound of formula (3) include: N- (Tallow) -N, N, N', N'-Tetramethyl-1,3-propanediammonium dimethosulfate, N- (Tallow) -N, N', N'-trimethyl-1,3- Propane diammonium dimethosulfate, N- (tallow) -N, N, N', N', N'-pentamethyl-1,3-propanediammonium dimethosulfate, N-oleyl-N, N, N', N', N'-pentamethyl-1,3-propanediammonium dimethosulfate, N-stearyl-N, N, N', N', N'-pentamethyl-1,3-propanediammonium dimethosulfate, N -Stearyloxypropyl-N, N', N'-tris (3-hydroxypropyl) -1,3-propanediammonium acetate.

[0015] Another class of preferred quaternary ammonium compounds has the following formula.

[Chemical 23]<img file="JP4046366B2_D0004.tif" />In the formula, A^-Has the above meaning, R₁₃Can be the same or different, each C₁-C₃₀Aliphatic residue, C₁-C₄Hydroxyalkyl, -C₂H₄OC (= O) -R₁, -C₂H₄NHC (= O) -R₁ , Or -CH₂CH [OC (= O) -R₁] [CH₂OC (= O) -R₁]. However, at least one R₁₃, Preferably two Rs₁₃Is C₁₄-C₃₀Alkyl, -C₂H₄OC (= O) -C₁₄-C₃₀Alkyl, -C₂H₄NHC (= O) -C₁₄-C₃₀Alkyl, or -CH₂CH [OC (= O) -C₁₄-C₃₀Alkyl] [CH₂OC (= O) -C₁₄-C₃₀Alkyl]. Preferably the remaining R₁₃Is C₁-C₄Alkyl, especially methyl or ethyl, or C₁-C₄Hydroxyalkyl, especially hydroxymethyl or hydroxyethyl.

[0016] Special examples of the preferred compound of formula (4) include: Distearyldimethylammonium chloride, dilauryldimethylammonium chloride, dihexadecyldimethylammonium chloride, distearyldimethylammonium bromide, distearyldimethylammonium metosulfate, distearyldi (isopropyl) ammonium chloride, distearyl (hydroxyethyl) methylammonium metsul Fert.

[0017] A preferred ester amidoamine cationic fabric softener has the following formula.

[Chemical 24]<img file="JP4046366B2_D0005.tif" />In the formula, R₁₃Has the above meaning, A₁Is anion A^-Is an inorganic or organic acid derived from it, A^-Has the above meaning. However, at least one R₁₃, Preferably two Rs₁₃Is C₁₄-C₃₀Alkyl, (CH₂)_nOC (= O) -C₁₄-C₃₀Alkyl, (CH₂)_nNHC (= O) -C₁₄-C₃₀Alkyl, or CH₂CH [OC (= O) -C₁₄-C₃₀Alkyl] [CH₂OC (= O) -C₁₄-C₃₀Alkyl], where n has the above meaning. Preferably the remaining R₁₃Is C₁-C₄Alkyl, especially methyl or ethyl, or C₁-C₄Hydroxyalkyl, especially hydroxymethyl or hydroxyethyl. The preferred compound of formula (5) is 3-stearoylamide propyl-2-stearoyloxymethyl-methylamine hydrochloride.

The cationic, amphoteric, or anionic optical brighteners used can be one or more of a wide range of cationic, amphoteric, or anionic optical brighteners, in particular λ =. It easily absorbs ultraviolet rays in the range of 280 to 400 nm and converts the absorbed energy into a non-jamming stable compound or a non-jamming form of energy by a chemical intermediate reaction. Cationic, amphoteric, or anionic optical brighteners are preferably phased with a rinse cycle cloth protectant.<u style="single">Yong</u>It should be sex and should be able to be absorbed on the washed textile material during the rinse cycle cloth protection treatment.

[0019] Cation optical brighteners are preferably of the bistilylphenyl class or phosphinate class, and amphoteric optical brighteners are preferably of the styrene or amine oxide class, which are negative. Ion optical brighteners are preferably of the class aminostilbene, dibenzofuranylbiphenyl or bistilylphenyl.

[0020] One preferred class of cationic bistylylphenyl optical brighteners has the following formula.

[Chemical 25]<img file="JP4046366B2_D0006.tif" />In the formula, Y is arylene, preferably 1,4-phenylene or 4,4'-diphenylene, each optionally substituted with chloro, methyl, or methoxy, q being 1 or 2, and R.₁₄Is hydrogen, chloro, C₁-C₄Alkyl, C₁-C₄Alkoxy, cyano, or C₁-C₄Alkoxycarbonyl, R₁₅And R₁₆Is C₁-C₄Alkyl, chloroethyl, methoxyethyl, β-ethoxyethyl, β-acetoxyethyl or β-cyanoethyl, benzyl, or phenylethyl, R₁₇Is C₁-C₄Alkyl, C₂-C₃Hydroxyalkyl, β-hydroxy-γ-chloropropyl, β-cyanoethyl, or C₁-C₄Alkoxycarbonylethyl, A^-Is an anion, R₁₇Is C₁-C₄When it is alkyl, A^-Is preferably an anion of chloride, bromide, iodide, metosulfate, etosulfate, benzenesulfonate, or p-toluenesulfonate, or R.₁₇Is β-hydroxy-γ-chloropropyl, β-cyanoethyl or C₁-C₄When it is alkoxycarbonylethyl, preferably A^-Is an anion of formate, acetate, propionate, or benzoate.

[0021] Preferred compounds of formula (6) have Y of 1,4-phenylene or 4,4'-diphenylene and R.₁₄Is hydrogen, methyl, or cyano, R₁₅And R₁₆Are methyl or cyano, respectively, and R₁₇And A have the above-mentioned preferable meanings. One particularly preferred compound of formula (6) has the following formula.

[Chemical 26]<img file="JP4046366B2_D0007.tif" />The compound of formula (6) and its manufacturing process are described in US Pat. No. 4,09193.

A more preferred class of cationic bistylylphenyl optical brighteners has the following formula.

[Chemical 27]<img file="JP4046366B2_D0008.tif" />In the formula, R₁₄And q have the above meanings, Y₁Is C₂-C₄It is alkylene or hydroxypropylene, R₁₈Is C₁-C₄Alkyl or R₁₉And R₁₈And R₁₉Form a pyrrolidine, piperidine, hexamethyleneimine, or morpholine ring with nitrogen bound to R₁₉Is C₁-C₄Alkyl or R₁₈And R₁₈And R₁₉Form a pyrrolidine, piperidine, hexamethyleneimine, or morpholine ring with nitrogen bound to R₂₀Is hydrogen, C₁-C₄Alkyl, C₃-C₄Alkenyl, C₁-C₄Alkoxycarbonylmethyl, benzyl, C₂-C₄Hydroxyalkyl, C₂-C₄Cyanoalkyl or R₁₈And R₁₉And together with the nitrogen atom to which they are attached form a pyrrolidine, piperidine, hexamethyleneimine, or morpholine ring, where A has the above meaning and p is 0 or 1.

A preferred compound of formula (8) has q of 1 and R.₁₄Is hydrogen, chlorine, C₁-C₄Alkyl, or C₁-C₄Alkoxy and Y₁In (CH₂)₂And R₁₈And R₁₉Are the same, each is methyl or ethyl, R₂₀Is methyl or ethyl, p is 1 and A is CH₃OSO₃Or C₂H₅OSO₃Is a compound. The compound of formula (8) and its manufacturing process are described in US Pat. No. 4,339,393.

A more preferred class of cationic bistylylphenyl optical brighteners has the following formula.

[Chemical 28]<img file="JP4046366B2_D0009.tif" />In the formula, R₁₄, Y₁, A, p and q have the above meanings, R₂₁And R₂₂Independently C₁-C₄Alkyl or C₂-C₃Alkenyl or R₂₁And R₂₂Form a pyrrolidine, piperidine, hexamethyleneimine, or morpholine ring with the nitrogen atom to which they are attached, and R₂₃Is hydrogen, C₁-C₄Alkyl, or C₂-C₃Alkenyl or R₂₁, R₂₂And R₂₃Form a pyridine or picoline ring with the nitrogen atom to which they are attached, Z is sulfur, -SO₂-,-SO₂NH-, -OC₁-C₄It is alkylene-COO- or -OCO-.

A preferred compound of formula (9) is R.₁₄Is hydrogen, chlorine, C₁-C₄Alkyl, or C₁-C₄Alkoxy and R₂₁And R₂₂Is independently C₁-C₄Form a pyrrolidine, piperidine, or morpholine ring with nitrogen atoms that are alkyl or to which they are attached, R₂₃Is hydrogen, C₁-C₄Alkyl, or C₃-C₄Alkenyl or R₂₁, R₂₂And R₂₃Form a pyridine ring with the nitrogen atom to which they are attached, Z is sulfur, -SO₂-, Or-SO₂It is a compound that is NH-. The compound of formula (9) and its manufacturing process are described in US Pat. No. 4,486,352.

A more preferred class of cationic bistylylphenyl optical brighteners has the following formula.

[Chemical 29]<img file="JP4046366B2_D0010.tif" />In the formula, R₁₄, R₂₁, R₂₂, R₂₃, Y₁, A, p and q have the above meanings. The preferred compound of formula (10) has q of 1 and R₁₄Is hydrogen, chlorine, C_1-4Alkyl, or C₁-C₄Alkoxy and R₂₁And R₂₂And independently C₁-C₄Forming a pyrrolidine, piperidine, or morpholine ring with a nitrogen atom that is alkyl or to which they are attached, R₂₃Is hydrogen, C₁-C₄Alkyl, or C₃-C₄Alkenyl or R₂₁, R₂₂And R₂₃Is a compound that forms a pyridine ring with the nitrogen atoms to which they are attached. The compound of formula (10) and its manufacturing process are described in US Pat. No. 4,602,87.

[0027] One preferred class of amphoteric styrene optical brighteners has the following equation:

[Chemical 30]<img file="JP4046366B2_D0011.tif" />In the formula, R₁₄, R₂₁, R₂₂, Y₁And q have the above meanings, Z₁Is oxygen, sulfur, direct bond, -COO-, -CON (R)₂₄)-Or -SO₂N (R₂₄)-And here R₂₄Is hydrogen, C₁-C₄Alkyl or cyanoethyl, Q is -COO- or -SO₃---. The preferred compound of formula (11) is Z₁Is oxygen, direct bond, -CONH-, -SO₂NH-, or -COO-, especially oxygen, q is 1, R₂₁Is hydrogen, C₁-C₄Alkyl, methoxy, or chlorine, R₂₂, R₂₃, Y₁And Q are compounds having the above meaning. The compound of formula (11) and its manufacturing process are described in US Pat. No. 4,478,598.

[0028] One preferred class of amine oxide optical brighteners has the following formula.

[Chemical 31]<img file="JP4046366B2_D0012.tif" />In the formula, q has the above meaning, B is a whitening agent group selected from 4,4'-dystylylbiphenyl, 4,4'-divinylstilbene, and 1,4'-dystylylbenzene, respectively. Halogen, C if desired₁-C₄Alkyl, C₁-C₄Hydroxyalkyl, C₁-C₄Halogenoalkyl, C₁-C₄Cyanoalkyl, C₁-C₄Alkoxy-C₁-C₄Alkyl, Phenyl-C₁-C₄Alkyl, carboxy-C₁-C₄Alkyl, Carbo-C₁-C₄Alkoxy-C₁-C₄Alkyl, C₁-C₄Alkenyl, C₅-C₈Cycloalkyl, C₁-C₄Alkoxy, C₂-C₄Alkenoxy, C₁-C₄Alkoxycarbonyl, carbamoyl, cyano, C₁-C₄Alkylsulfonyl, phenylsulfonyl, C₁-C₄Replaced by 1 to 4 substituents selected from alkoxysulfonyl, sulfamoyl, hydroxyl, carboxyl, sulfo and trifluoromethyl, Z₂Is B and Y₂Direct bond with, oxygen atom, sulfur atom, -SO₂-,-SO₂O-, -COO-, -CON (R₂₇)-Or-SO₂N (R₂₇)-And here R₂₇Is hydrogen, or optionally halogen, cyano, hydroxyl, C₂-C₅Carboalkoxy, C₁-C₄C substituted with alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl, or sulfamoyl₁-C₄Alkyl and Y₂Is C₂-C₄Alkylene or C₂-C₄Alkyleneoxy-C₂-C₄It is alkylene, respectively halogen, hydroxyl, C if desired.₂-C₅Carboalkoxy, C₁-C₄Substituted with alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl, or sulfamoyl, R₂₅And R₂₆Independently C₅-C₈Cycloalkyl, C₁-C₄Alkyl, or phenyl, respectively, optionally halogen, hydroxyl, C₂-C₅Carboalkoxy, C₁-C₄Substituted with alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl, or sulfamoyl, in all carbamoyl or sulfamoyl groups described above, the nitrogen atom is optionally one or two Cs.₁-C₄Alkyl, C₁-C₄Hydroxyalkyl, C₂-C₅Cyanoalkyl, C₁-C₄It is substituted with a halogenoalkyl, benzyl, or phenyl group.

[0029] The preferred whitening agent group B has the following formula.

[Chemical 32]<img file="JP4046366B2_D0013.tif" />In the formula, q has the above meaning and the ring is optionally substituted as described above. Preferred Z₂Is oxygen, -SO₂-, Or-SO₂N (R₂₈)-And here R₂₈C substituted with hydrogen, or optionally hydroxyl, halogen, or cyano₁-C₄Alkyl and R₂₅And R₂₆Independently, optionally halogen, cyano, hydroxyl, C₁-C₄Alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, or C₂-C₅C substituted with alkoxycarbonyl₁-C₄It is alkyl. Another preferred compound of formula (10) is Z₂Is oxygen, sulfur, -SO₂-, -CON (R₂₈)-Or-SO₂N (R₂₈)-And R₂₈C substituted with hydrogen, or optionally hydroxyl, halogen, or cyano₁-C₄Alkyl and Y₂Is C₁-C₄It is a compound that is alkylene. The compound of formula (12) and its manufacturing process are described in US Pat. No. 4,5969161.

[0030] One preferred class of cationic phosphinate optical brighteners has the following formula.

[Chemical 33]<img file="JP4046366B2_D0014.tif" />In the equation, q has the above meaning, B₁Is a whitening agent group, Z₃Is a direct join, -SO₂-C₂-C₄-Alkyleneoxy, -SO₂-C₂-C₄Alkylene-COO-, -SO₂-, -COO-, -SO₂-C₂-C₄Alkylene -CON (R)₃₃)-Or-SO₂N (R₃₃)-And here R₃₃C substituted with hydrogen, or optionally hydroxyl, halogen, or cyano₁-C₄Alkyl and R₂₈Halogen, cyano, hydroxyl, C if desired₁-C₄Alkoxycarbonyl or C₁-C₄C substituted with alkylcarbonyloxy₁-C₄Alkyl or C₂-C₄Alkenyl or R₂₈Is halogen, C if desired₁-C₄Alkyl or C₁-C₄Benzyl substituted with alkoxy, or R₂₈Is R₂₉And together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine group, R₂₉Halogen, cyano, hydroxyl, C if desired₁-C₄Alkoxycarbonyl or C₁-C₄C substituted with alkylcarbonyloxy₁-C₄Alkyl or C₂-C₄Alkenyl or R₂₉Is halogen, C if desired₁-C₄Alkyl or C₁-C₄Benzyl substituted with alkoxy, or R₂₉Is R₂₈And together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine group, R₃₀Is C₁-C₄Alkyl and R₃₁Is hydrogen, or optionally cyano, hydroxyl, C₁-C₄Alkoxycarbonyl or C₁-C₄C substituted with alkylcarbonyloxy₁-C₄Alkyl and R₃₂Is C₁-C₄It is alkyl.

[0031] Preferably, the whitening agent group B₁Is the following formula [Chemical expression 34]<img file="JP4046366B2_D0015.tif" />Or it has the following equation.

[Chemical 35]<img file="JP4046366B2_D0016.tif" />Each equation is optionally halogen, C₁-C₄Alkyl, C₁-C₄Hydroxyalkyl, C₁-C₄Halogenoalkyl, C₁-C₄Cyanoalkyl, C₁-C₄Alkoxy-C₁-C₄Alkyl, Phenyl-C₁-C₄Alkyl, carboxy-C₁-C₄Alkyl, Carbo-C₁-C₄Alkoxy-C₁-C₄Alkyl, C₂-C₄Alkenyl, C₅-C₈Cycloalkyl, C₁-C₄Alkoxy, C₂-C₄Alkenoxy, C₁-C₄Alkoxycarbonyl, carbamoyl, cyano, C₁-C₄Alkyl-sulfonyl, phenylsulfonyl, C₁-C₄It is substituted with 1 to 4 substituents selected from alkoxysulfonyl, sulfamoyl, hydroxyl, carboxyl, sulfo and trifluoromethyl. The compound of formula (13) and the method for producing the compound are described in GB-A-2023605.

The bis (triazinyl) diaminostilbene anionic fluorescent whitening agent preferred for use in the present invention has the following formula.

[Chemical 36]<img file="JP4046366B2_D0017.tif" />A preferred dibenzofuranylbiphenyl anion optical brightener for use in the present invention has the following formula.

[Chemical 37]<img file="JP4046366B2_D0018.tif" />[0034] The anionic bistylylphenyl fluorescent whitening agent preferable for use in the present invention has the following formula.

[Chemical 38]<img file="JP4046366B2_D0019.tif" />In equations (14) to (16), R₃₃Is one or two SOs as desired₃Phenyl substituted with M group, R₃₄Is NH-C₁-C₄Alkyl, N (C₁-C₄Alkyl)₂, NH-C₁-C₄Alkoxy, N (C₁-C₄Alkoxy)₂, N (C₁-C₄Alkyl) (C₁-C₄Hydroxyalkyl) or N (C)₁-C₄Hydroxyalkyl)₂And R₃₅Is H, C₁-C₄Alkyl, CN, Cl or SO₃M and R₃₆And R₃₇Are independently H, C₁-C₄Alkyl, SO₃M, CN, Cl or OC₁-C₄Alkyl, but R₃₅, R₃₆And R₃₇At least two of them are SO₃M, the third group is solubilized, R₃₈Is H, SO₃M, OC₁-C₄Alkyl, CN, Cl or COO-C₁-C₄Alkyl or CON (C₁-C₄Alkyl)₂And M is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C₁-C₄Alkylammonium, mono-, di- or tri-C₁-C₄Hydroxyalkylammonium, or C₁-C₄Alkyl and C₁-C₄Ammonium di- or tri-substituted with a mixture of hydroxyalkyl groups, where r is 0 or 1. In the compounds of formulas (14) to (16), C₁-C₄Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl and n-butyl, especially methyl. The aryl group is naphthyl, or especially phenyl.

A preferred special example of equation (14) has the following equation:

[Chemical 39]<img file="JP4046366B2_D0020.tif" />[Chemical 40]<img file="JP4046366B2_D0021.tif" />[Chemical 41]<img file="JP4046366B2_D0022.tif" />A preferred example of the compound of formula (15) has the following formula.

[Chemical 42]<img file="JP4046366B2_D0023.tif" />[Chemical 43]<img file="JP4046366B2_D0024.tif" />[Chemical 44]<img file="JP4046366B2_D0025.tif" />[Chemical 45]<img file="JP4046366B2_D0026.tif" />A preferred example of the compound of formula (16) has the following formula.

[Chemical 46]<img file="JP4046366B2_D0027.tif" />[Chemical 47]<img file="JP4046366B2_D0028.tif" />[Chemical 48]<img file="JP4046366B2_D0029.tif" />The compounds of formulas (14) to (16) are known and can be obtained by known methods.

[0036] The composition of the present invention may contain a small amount of one or more auxiliary agents in addition to the fluorescent whitening agent. Examples of auxiliaries are emulsifiers, fragrances, color dyes, opalescent agents, UV absorbers, bactericides, nonionic surfactants, alkali metal nitrites or nitrates, especially anti-gelling agents such as sodium nitrate, Kay. Examples include corrosion inhibitors such as sodium silicate. The amount of each of this desired adjunct should not exceed 2% by weight of the composition.

[0037] As a third feature, the present invention also comprises 0.3-10% by weight of a cationic, amphoteric or anionic optical brightener relative to the total weight of the composition and optionally a cloth protective component. Provided is a method for treating a cloth article, which comprises applying a cloth rinse composition containing and substantially water in the balance to a pre-washed article. Preferably, the fabric protective ingredient is a fabric softener, stain remover or stain preventive or waterproof, preferably 5-25% by weight, particularly 10-20% by weight, based on the total weight of the composition. Exists in the amount of.

[0038] Preferred methods for treating fabric articles are 5-25% by weight, preferably 10-20% by weight of cationic fabric softener and 0.3-10% by weight, preferably 0.3-10% by weight, based on the total weight of the composition. Applying a rinse cycle fabric softener composition containing 0.3 to 3% by weight of cation, amphoteric or anionic optical brightener and the balance being substantially water to a pre-washed fabric article. Includes. Cloth articles processed by the methods of the invention can be from any type of fiber, such as wool, polyamide, cotton, polyester, polyacrylic, silk, or mixtures thereof. The methods and compositions of the present invention not only provide improved SPF to washed fabric articles, thereby providing increased protection to the skin, but also, for example, for fabric articles treated in this way. By improving tear strength and light resistance, it also increases the useful life of the fabric articles treated according to the present invention. Hereinafter, the present invention will be further described with reference to the following examples.

【0039】<u style="single">Example 1</u>The following rinse cycle softener-based compositions were prepared. Distearyldimethylammonium chloride (70% active ingredient) 7.0 g Fatty alcohol ethoxylate 0.5 g Deionized water 92.5 g To this, 0.3 g, 0.9 g, or 2.7 g of the amphoteric optical brightener of the following formula was added, respectively.

[Chemical 49]<img file="JP4046366B2_D0030.tif" /> 【0040】<u style="single">Example 2</u>The following rinse cycle softener-based compositions were prepared. Distearyldimethylammonium chloride 7.0 g Fatty alcohol ethoxylate 0.5 g Deionized water 92.5 g To this, 0.3 g, 0.9 g, or 2.7 g of the cationic fluorescent whitening agent of the following formula was added, respectively.

[Chemical 50]<img file="JP4046366B2_D0031.tif" /> 【0041】<u style="single">Examples 3 and 4</u> First, apply 5g of cotton cloth at 60 ° C.<u style="single">bath</u>Washed with 4 g / liter of ECE standard detergent at a ratio of 1:20. The washed items were then rinsed and treated with a rinse softener while still moist. The amount of rinse cycle softener base composition of Example 1 or 2 was used in an amount of 5 g / liter. Using tap water<u style="single">bath</u>Treatment was performed at a ratio of 1:40 at 25 ° C for 10 minutes. The fabric softener-treated product was then centrifuged at 60 ° C. The whiteness and SPF value of the dried softener-treated product were measured. The dried fabric softener-treated item was then rewashed using the same detergent and washing conditions used for the initial wash. However, after rinsing, the rewashed item was centrifugally dried at 60 ° C without rinsing and softening. The whiteness and SPF value of the rewashed and dried product were measured. The whiteness of each of the dried products was measured using a DCI / SF500 spectrophotometer according to Ganz's method. Ganz's method is described in detail in Ciba-Geigy Review, 1973/1, and the Journal of Color and Appearance, 1, No. 5 (1972) ISCC Conference on Fluorescence and the Colorimetry of Fluorescent Materials, Williamsburg, February 1972, also described in the paper "Whiteness Measurement". Sun protection (SPF) was determined by measuring UV rays transmitted through the sample using a double lattice spectrophotometer equipped with an Ulbricht bowl. The calculation of SPF is BL Diffey, J.Robson, J.Soc. Cosm. Chem.,<u style="single">40</u>(1989), pp.130-131. The results are shown in the following table.

[table 1]<img file="JP4046366B2_D0032.tif" /> FWA (optical brightener) concentration means the concentration of active FWA compound relative to the total weight of the rinse formulation. The results in the table show improvements in Gauz whiteness (GW) and SPF values of cotton substrates treated with the rinse composition of the present invention, both before and after rewashing. Similar results were obtained when the optical brightener used in Example 1 or 2 was replaced by any of the following equations.

[Chemical 51]<img file="JP4046366B2_D0033.tif" />