KR910002919B1 - Bleaching improving agent - Google Patents

Bleaching improving agent Download PDF

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Publication number
KR910002919B1
KR910002919B1 KR1019860006465A KR860006465A KR910002919B1 KR 910002919 B1 KR910002919 B1 KR 910002919B1 KR 1019860006465 A KR1019860006465 A KR 1019860006465A KR 860006465 A KR860006465 A KR 860006465A KR 910002919 B1 KR910002919 B1 KR 910002919B1
Authority
KR
South Korea
Prior art keywords
bleaching
acid
present
bleach
enhancer
Prior art date
Application number
KR1019860006465A
Other languages
Korean (ko)
Other versions
KR870002323A (en
Inventor
나오끼 고오찌까
Original Assignee
가오오 가부시끼가이샤
마루다 요시오
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 가오오 가부시끼가이샤, 마루다 요시오 filed Critical 가오오 가부시끼가이샤
Publication of KR870002323A publication Critical patent/KR870002323A/en
Application granted granted Critical
Publication of KR910002919B1 publication Critical patent/KR910002919B1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0605—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two belts, e.g. Hazelett-process
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B61—RAILWAYS
    • B61B—RAILWAY SYSTEMS; EQUIPMENT THEREFOR NOT OTHERWISE PROVIDED FOR
    • B61B13/00—Other railway systems
    • B61B13/12—Systems with propulsion devices between or alongside the rails, e.g. pneumatic systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0637—Accessories therefor
    • B22D11/068—Accessories therefor for cooling the cast product during its passage through the mould surfaces
    • B22D11/0685—Accessories therefor for cooling the cast product during its passage through the mould surfaces by cooling the casting belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/14—Closures
    • B22D41/22—Closures sliding-gate type, i.e. having a fixed plate and a movable plate in sliding contact with each other for selective registry of their openings
    • B22D41/28—Plates therefor
    • B22D41/34—Supporting, fixing or centering means therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
    • B25C—HAND-HELD NAILING OR STAPLING TOOLS; MANUALLY OPERATED PORTABLE STAPLING TOOLS
    • B25C5/00—Manually operated portable stapling tools; Hand-held power-operated stapling tools; Staple feeding devices therefor
    • B25C5/02—Manually operated portable stapling tools; Hand-held power-operated stapling tools; Staple feeding devices therefor with provision for bending the ends of the staples on to the work
    • B25C5/0285—Hand-held stapling tools, e.g. manually operated, i.e. not resting on a working surface during operation
    • B25C5/0292—Hand-held stapling tools, e.g. manually operated, i.e. not resting on a working surface during operation with the objects to be stapled together introduced perpendicularly to the longitudinal axis of the tool in an opening formed by an anvil and a plunger
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
    • B27K3/0292—Processes; Apparatus involving an additional treatment during or after impregnation for improving fixation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/22—Compounds of zinc or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/001—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41F—PRINTING MACHINES OR PRESSES
    • B41F13/00—Common details of rotary presses or machines
    • B41F13/08—Cylinders
    • B41F13/10—Forme cylinders
    • B41F13/12—Registering devices
    • B41F13/14—Registering devices with means for displacing the cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41F—PRINTING MACHINES OR PRESSES
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    • B41F13/08—Cylinders
    • B41F13/10—Forme cylinders
    • B41F13/12—Registering devices
    • B41F13/16—Registering devices with means for displacing the printing formes on the cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
    • B60B39/00—Increasing wheel adhesion
    • B60B39/003—Vehicle mounted non-skid chains actuated by centrifugal force
    • B60B39/006—Vehicle mounted non-skid chains actuated by centrifugal force characterised by a control system for the actuation of the rotating chain wheel
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B60W10/11—Stepped gearings
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B60W—CONJOINT CONTROL OF VEHICLE SUB-UNITS OF DIFFERENT TYPE OR DIFFERENT FUNCTION; CONTROL SYSTEMS SPECIALLY ADAPTED FOR HYBRID VEHICLES; ROAD VEHICLE DRIVE CONTROL SYSTEMS FOR PURPOSES NOT RELATED TO THE CONTROL OF A PARTICULAR SUB-UNIT
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    • B60W30/18—Propelling the vehicle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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    • B65B55/022—Sterilising, e.g. of complete packages of flexible containers having a filling and dispensing spout, e.g. containers of the "bag-in-box"-type
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B65B7/02—Closing containers or receptacles deformed by, or taking-up shape, of, contents, e.g. bags, sacks
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C—CHEMISTRY; METALLURGY
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    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C22C1/0441—Alloys based on intermetallic compounds of the type rare earth - Co, Ni
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Abstract

내용 없음.No content.

Description

[발명의 명칭][Name of invention]

표백 증진제Bleach enhancers

[발명의 상세한 설명]Detailed description of the invention

본 발명은 셀룰로오스계 섬유용 표백증진제에 관한 것이다. 더욱 상세히 말하면, 본 발명은 셀룰로오스계 섬유 표백욕(fiber bleaching bath)이 경도 성분등의 표백 저해 인자를 함유하고 있는 경우, 보다 높은 백도(白度), 감촉, 봉제성을 부여할 수 있는 셀룰로오스계 섬유용 표백증진제에 관한 것이다.The present invention relates to a bleach enhancer for cellulose fibers. More specifically, the present invention is a cellulose-based system that can give higher whiteness, texture, and sewing properties when the cellulose fiber bleaching bath contains bleach inhibitory factors such as hardness components. It relates to a bleach enhancer for textiles.

종래의 기술을 설명하면 다음과 같다. 통상적으로 천연 색소는 섬유를 정련하고 표백한 후라도 셀룰로오스계 섬유에 그대로 잔류한다. 마찬가지로 착색 물지로 남아 있다.The prior art is described as follows. Typically, natural pigments remain in the cellulosic fibers even after the fibers have been refined and bleached. Similarly, it remains a coloring matter.

종래의 표백법은 과산화표백, 염소 표백, 아염소산나트륨 표백등이 있으나, 그중에 과산화표백은 섬유를 손상시키지 않고 표백을 할 수 있으며, 조작도 간편하고 백도 보존성이 길기 때문에 통상적으로 광범위하게 이용되어 왔다. 과산화표백은 과산화물에서 분해되는 발생기 산소를 이용하여 셀룰로오스계 섬유중의 색소를 산화 및 분해하여 이루어진다. 이 산화 분해는 pH가 알카리성인 환경에서 이루어지는 것이 효과적이기때문에, 수산화나트륨과 같은 알카리제가 병용되고, 또한 규산나트륨은 알카리하에서 과산화수소 분해의 안정제로서 역시 사용된다. 따라서 표백 조성물은 과산화수소, 알카리(수산화나트륨등) 및 규산나트륨(몰비로 SiO2: Na2O=2.5 : 1)로 구성되어 있다. 조성물을 이용하여 셀룰로오스계 섬유를 표백하는 경우에, 사용하는 물의 경도가 높으면, 규산나트륨은 수중의 경도성분과 결합되어, 규산칼슘과 규산마그네슘과 같은 물에 불용성인 규산염이 생성되며, 이것은 섬유위에 부착되어 포(cloth)의 백도를 향상시키지 못하고, 촉감도 딱딱하고 거칠게하며, 미싱 바늘과의 마찰계수가 커져서 봉제성에 지장을 초래하였다. 따라서, 이상과 같은 문제점 해결이 요망되고 있다. 이 문제점을 개선하기 위하여 에틸렌디아민 테트라아세트산, 디에틸렌트리아민 펜타아세트산, 하이드록실에틸렌디아민 트리아세트산, 니트릴로 트리아세트산, 트리폴리인산 나트륨등을 병용하여 사용하는 경우도 있지만, 그의 효과가 반드시 충분한 것은 아니며, 현상태에서 문제점의 근본적인 해결책을 제공할 수 없었다.Conventional bleaching methods include peroxide bleaching, chlorine bleaching, sodium chlorite bleaching, etc. Among them, bleaching peroxide can be bleached without damaging the fiber, and it has been commonly used widely because of its easy operation and long white preservation. . Bleaching is achieved by oxidizing and decomposing the pigment in the cellulosic fibers using generator oxygen decomposed from the peroxide. Since this oxidative decomposition is effective in an alkaline pH environment, an alkali agent such as sodium hydroxide is used in combination, and sodium silicate is also used as a stabilizer for hydrogen peroxide decomposition under alkali. Therefore, the bleaching composition is composed of hydrogen peroxide, alkali (such as sodium hydroxide) and sodium silicate (SiO 2 : Na 2 O = 2.5: 1 in molar ratio). In the case of bleaching cellulose fibers using the composition, when the hardness of water to be used is high, sodium silicate is combined with hardness components in water, producing silicates insoluble in water such as calcium silicate and magnesium silicate, which It does not improve the whiteness of the cloth, makes the touch hard and coarse, and increases the coefficient of friction with the sewing needle, causing trouble in sewing. Therefore, the above problem solving is desired. In order to improve this problem, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, hydroxylethylenediamine triacetic acid, nitrilo triacetic acid, sodium tripolyphosphate, etc. may be used in combination, but the effect is not necessarily sufficient. In the current state, they could not provide an essential solution of the problem.

더욱이 과산화수소 표백에 있어서는, 금속이온, 특히 철, 동, 망간등과의 접촉으로 인한 셀룰로오스계 섬유의 취화(embrittlement)의 문제가 있다. 즉, 표백공정중에 사용하고 있는 물이나 장치에 들어 있는 금속이온(주로 철이온) 또는 철녹이 원인이 되는 과산화수소의 분해가 촉진되어, 셀룰로오스계 섬유 편직포위에 면도칼자국(면도칼로 절단하여 형성된 긁힌자국) 또는 바늘구멍이 생기는 문제점이 있었다. 이 문제점을 개선하기 위하여, 아미노 카르복실레이트계 유기 킬레이트제, 특히 디에틸렌트리아민 펜타아세트산 등을 첨가하는 것이 시도되었으나, 이와 같은 킬레이트제는 고 pH 영역(알카리측)에는 철이온에 관한 킬레이트 효과를 보이지 않기 때문에, 알카리 영역에서 이루어진 통상의 과산화수소표백에 있어서는 효과적이지 못하다. 이와 같은 상태에서, 고 pH 영역에서 철에 관한 킬레이트 효과를 보이는 당알코올 또는 알돈산등을 아미노카르복실레이트계 유기 킬레이트계와 병용하는 경우(특허공고번호 30184/1986와 30185/1986)도 있지만, 그 효과는 반드시 충분치는 않고 현 상태로는 발본적인 해결까지는 이르지 못하고 있다. 지금까지 본 발명자들은 셀룰로오스계 섬유의 전술한 표백 불량의 문제점을 해결하는데 진지한 연구를 한 결과, 특정의 폴리카르복실산과 당알코올 및/또는 알돈산을 병용하여 상기의 문제점을 해결할 수 있다는 것을 발견하여 본 발명을 완성하였다.Moreover, in hydrogen peroxide bleaching, there is a problem of embrittlement of cellulose fibers due to contact with metal ions, in particular iron, copper, manganese and the like. That is, the decomposition of hydrogen peroxide, which causes metal ions (primarily iron ions) or iron rust in water and equipment used during the bleaching process, is promoted, and a razor cut (cut by cutting with a razor blade) on the cellulose fiber knitted fabric. ) Or there was a problem that the needle hole. In order to improve this problem, it has been attempted to add an amino carboxylate organic chelating agent, especially diethylenetriamine pentaacetic acid and the like, but such a chelating agent has a chelate effect on iron ions in the high pH region (alkali side) Since it is not shown, it is not effective in normal hydrogen peroxide bleaching made in the alkaline region. In such a state, in the case of using a sugar alcohol or aldonic acid or the like having an chelating effect on iron in the high pH region together with an aminocarboxylate organic chelate system (Patent Publication Nos. 30184/1986 and 30185/1986), The effects are not necessarily sufficient and are not attained to a radical solution in their present state. Until now, the present inventors have made serious studies in solving the problems of the above-mentioned bleaching defects of cellulose fibers, and found that the above problems can be solved by using a combination of a specific polycarboxylic acid and sugar alcohol and / or aldonic acid. The present invention has been completed.

본 발명의 표백 증진제는 셀룰로오스계 섬유에 적합하고, (a) 말레산, 아크릴산 또는 메타크릴산의 중합체, 공중합체 또는 그의 염과 : (b-1) 일반식 CH2OH(CHOH)nCH2OH인 사카로오스알코올 : (식중 n은 2 내지 6의 정수이다)(b-2) 일반식 CH2OH(CHOH)nCOOH인 알돈산 : (식중 n은 2 내지 6의 정수이다)(b-3) 알코올 또는 산의 수용성염 : 또는 (b-4) 알코올 또는 산의 락톤 : 으로 구성된다.The bleach enhancer of the present invention is suitable for cellulose fibers, and (a) a polymer, copolymer or salt thereof of maleic acid, acrylic acid or methacrylic acid: (b-1) general formula CH 2 OH (CHOH) n CH 2 Saccharose alcohol which is OH: (wherein n is an integer of 2 to 6) (b-2) Aldonic acid which is a general formula CH 2 OH (CHOH) n COOH: (wherein n is an integer of 2 to 6) (b-3 A) water-soluble salts of alcohols or acids; or (b-4) lactones of alcohols or acids.

즉, 본 발명은 다음 (a)와 (b)로 구성되며 셀룰로오스계 섬유용 표백 증진제를 제공한다.(a) 말레산, 아크릴산, 메타크릴산으로 구성되는 군으로부터 선택된 1종 또는 그 이상의 성분을 구성단위로 하는 중합체, 공중합체, 또는 그의 염과, (b) 일반식 CH2OH(CHOH)nCH2OH로 표시되는 당알코올(식중 n은 2 내지 6의 정수이다) 및/또는 일반식 CH2OH(CHOH)nCOOH로 표시되는 알돈산(식중 n은 2 내지 6의 정수이다.), 그의 수용성염 또는 그의 락톤.That is, the present invention is composed of the following (a) and (b) and provides a bleach enhancer for cellulose fibers. (A) at least one component selected from the group consisting of maleic acid, acrylic acid and methacrylic acid A polymer, a copolymer, or a salt thereof as the structural unit, and (b) a sugar alcohol represented by the general formula CH 2 OH (CHOH) n CH 2 OH (wherein n is an integer of 2 to 6) and / or a general formula Aldonic acid represented by CH 2 OH (CHOH) n COOH (wherein n is an integer from 2 to 6), its water soluble salt or its lactone.

본 발명의 표백증진제중의 (a)성분으로서는 수 평균 분자량이 300 내지 8000인 것이 바람직하다. 본 발명에서 사용가능한 성분(a)로서의 염에는 알카리 금속염, 암모늄염, 또한 디에탄올 아민과 트리에탄올 아민과 같은 알칸올 아민염등이 포함되며, 성능을 저하시키지 않는 정도로 미중화된 부분이 잔류할 수 있다. 더욱이 성능을 저하시키지 않을 정도로 성분(a)로서 사용가능한 중합체 또는 공중합체는 말레산, 아크릴산, 메타크릴산 이외의 단량체를 공중합하여 얻게 되는 것이 포함될 수 있으며, 사용가능한 이와 같은 단량체에는 아크릴아미드, 메타크릴술폰산 또는 비닐 술폰산과 같은 각종의 술폰산, 아크릴산 2-히드록시에틸, 각종의 아크릴산 에스테르, 각종의 메타크릴산 에스테르, N-메틸롤아크릴 아미드 또는 기타의 공중합이 가능한 물질이 포함될 수 있다. 본 발명의 표백증진제중의 (b)성분인 일반식 CH2OH(CHOH)nCH2OH로표시되는 당알코올로서는 예를 들면 D-소로비톨, D-만니톨, D-크실리롤 및 에리트로만녹티롤을 들 수있다. 더욱이, 일반식 CH2OH(CHOH)nCOOH로 표시되는 알돈산으로서는 예를 들면, D-만노즈, D-크실로즈 및 D-글루코스등과 같은 알돈산로부터 얻은 알돈산을 들 수 있다. 또한 이와 같은 산의 수용성 염예를 들면, 나트륨염 및 칼륨염 또는 이와 같은 산의 락톤을 사용할 수 있다.As (a) component in the bleaching enhancer of this invention, it is preferable that number average molecular weights are 300-8000. Salts as component (a) usable in the present invention include alkali metal salts, ammonium salts, and alkanol amine salts such as diethanol amines and triethanol amines, and the like, and may be unneutralized to a degree that does not degrade performance. . Moreover, polymers or copolymers usable as component (a) to such an extent that performance will not be impaired may include those obtained by copolymerizing monomers other than maleic acid, acrylic acid, methacrylic acid, and such monomers usable include acrylamide, meta Various sulfonic acids such as krillsulfonic acid or vinyl sulfonic acid, 2-hydroxyethyl acrylate, various acrylic esters, various methacrylic esters, N-methylol acrylamide or other copolymerizable materials may be included. Examples of the sugar alcohol represented by the general formula CH 2 OH (CHOH) n CH 2 OH in the bleach enhancer of the present invention include D-sorbitol, D-mannitol, D-xylol and erythro Mannotirol. Furthermore, as the aldonic acid represented by the general formula CH 2 OH (CHOH) n COOH, for example, there may be mentioned aldonic acids derived from aldonic acids such as D- mannose, D- keusil Rose and D- glucose. It is also possible to use water-soluble salts of such acids, for example sodium and potassium salts or lactones of such acids.

본 발명의 셀룰로오스계 섬유용 표백증진제는 전기한 (a) 및 (b)성분을 병용하며, 이때 (a)성분과 (b)성분의 혼합비는 중량비로 (a) : (b)=10∼90 : 90∼10의 범위가 바람직하며, 보다 바람직한 범위는 (a) : (b)=40∼60 : 60∼40이다. 본 발명의 셀룰로오스계 섬유용 표백증진제는 그 성능을 저하시키지 않을 정도로 음이온성, 양이온성 및 비이온성 계면활성제를 포함할 수 있다. 본 발명의 셀룰로오스계 섬유용 표백증진제에 함입될 수 있는 계면활성제로는 폴리옥시에틸렌 알킬에테르, 폴리옥시에틸렌 알킬아민, 황산 폴리옥시에틸렌 알킬에테르, 황산지방산 에스테르, 벤타인형 양성 활성제등을 예로 들수 있다. 본 발명의 표백증진제의 사용량은, 일반적으로 표백욕으로 0.01 내지 20g(고형분으로 환산하여)/1, 바람직하게는 0.04 내지 10g(고형분 환산)/1의 범위에 있다. 본 발명의 표백증진제를 적용할 수 있는 셀룰로오스계 섬유로는 면과 린넨과 같은 천연 셀룰로오스계 섬유에 부가해서, 이와 같이 천연 셀룰로오스계 섬유와 나일론, 폴리에스테르, 아크릴과 같은 합성섬유와의 혼합섬유, 아세테이트와 같은 반합성섬유와의 혼합섬유, 레이온과 쿠프타와 같은 재생섬유와의 혼합섬유를 들 수 있다.The bleaching enhancer for cellulose fibers of the present invention uses the aforementioned components (a) and (b), wherein the mixing ratio of the components (a) and (b) is (a) :( b) = 10 to 90 by weight ratio. The range of: 90-10 is preferable, and a more preferable range is (a) :( b) = 40-60: 60-40. The bleach enhancer for cellulose fibers of the present invention may include anionic, cationic and nonionic surfactants to such an extent that the performance thereof is not impaired. Examples of the surfactant that can be incorporated into the cellulose fiber bleach enhancer of the present invention include polyoxyethylene alkyl ether, polyoxyethylene alkylamine, sulfate polyoxyethylene alkyl ether, sulfuric acid fatty acid ester, and betaine type active agent. . The amount of the bleach enhancer of the present invention is generally in the range of 0.01 to 20 g (in terms of solids) / 1, preferably 0.04 to 10 g (in terms of solids) / 1 in a bleaching bath. Cellulose fibers to which the bleach enhancer of the present invention can be applied include, in addition to natural cellulose fibers such as cotton and linen, such mixed fibers of natural cellulose fibers and synthetic fibers such as nylon, polyester, and acryl, Mixed fibers with semi-synthetic fibers such as acetate, and mixed fibers with regenerated fibers such as rayon and coupta.

더욱이, 표백할때의 형태도, 즉 섬유, 얀, 슬라이버 치즈, 직물, 편물, 부직포, 더 나아가, 의류, 침구류등과 같은 최종 섬유 제품등의 어느 형태에 있어서도 지장이 없다. 셀룰로오스계 섬유 표백법으로서는 종래의 방법을 적용할 수 있으며, 이와 같은 방법으로는 패드스팀법, 가압저비법, 60℃ 내지 100℃까지 온도에서의 침지법이나 기타 방법등이 적용가능하다. 게다가, 본 발명의 표백증진제는, 지금까지 서술해온 표백뿐만 아니 라 정련-표백, 발호-정련-표백(desizing-scouring-bleaching)등과 같은 기타의 공정과 동시에 수행되는 표백에도 적용할 수 있다. 셀룰로오스계 섬유의 표백을, 과산화수소, 알카리 및 규산나트륨과 본 발명의 표백증진제와 공존되도록 하여 수행함으로써 물의 경도가 높은 경우나 또는 수중에 과산화수소의 분해를 촉진하는 철이온과 같은 금속이온이 포함되어 있는 경우에 있어서의 종래 표백법과 비교해보면, 섬유에 우수한 백도, 촉감, 봉제성이 부여할 수 있다. 셀룰로오스계 섬유의 표백시에 과산화수소, 알카리 및 규산나트륨과 함께 본 발명의 표백증진제를 공존시켜서 표백불량의 문제점을 해소할 수 있는 기구는 반드시 명확하지는 않더라도, 본 발명의 표백증진제가 갖고 있는 우수한 금속이온 킬레이트 성능에 기인한다고 할 수 있다. 즉, 물의 경도가 높은 경우에는, 본 발명의 표백증진제가 경도 성분을 킬레이트하여 수용성물질형성을 방해하거나 또는 물과 섬유로부터 나오는 수용성 물질을 분산시켜 섬유에 재부착을 방지한다는 것이다. 계(system)내에 철이온과 같은 과산화수소의 분해 촉진 물질이 포함된 경우에는, 본 증진제가 금속이온을 킬레이트하거나 분산시켜 섬유와의 접촉을 방해한다.Moreover, the form in bleaching is not impaired in any form, such as fibers, yarns, sliver cheeses, textiles, knits, nonwovens, and even finished textile products such as clothing, bedding and the like. As the cellulose fiber bleaching method, a conventional method can be applied, and as such a method, a pad steam method, a pressurized low boiling method, an immersion method at a temperature of 60 ° C. to 100 ° C., or the like can be applied. In addition, the bleach enhancer of the present invention can be applied not only to the bleaching described above but also to bleaching performed simultaneously with other processes such as refining-bleaching, desizing-scouring-bleaching, and the like. The bleaching of cellulose fibers is carried out by coexisting with hydrogen peroxide, alkali and sodium silicate and the bleach enhancer of the present invention, which contains metal ions such as iron ions which promote the decomposition of hydrogen peroxide in high water hardness or in water. Compared with the conventional bleaching method in the case, excellent whiteness, feel, and sewing property can be imparted to the fiber. Although the mechanism which can cope with the problem of the bleaching defect by coexisting the bleach enhancer of this invention with hydrogen peroxide, alkali, and sodium silicate at the time of bleaching a cellulose fiber, the outstanding metal ion of the bleach enhancer of this invention is not necessarily clear. This may be due to the chelate performance. In other words, when the hardness of the water is high, the bleach enhancer of the present invention chelates the hardness component to prevent the formation of water-soluble substances or to disperse water-soluble substances from water and fibers to prevent reattachment to the fibers. If the system contains a substance that promotes the decomposition of hydrogen peroxide, such as iron ions, the enhancer chelates or disperses the metal ions to prevent contact with the fibers.

[실시예]EXAMPLE

아래에 배합실시예 및 가공실시예를 열거하여 본 발명을 구체적으로 설명하겠지만, 본 발명은 이와 같은 실시예에만 한정되는 것은 아니다.Although the present invention will be specifically described by enumerating the compounding examples and processing examples below, the present invention is not limited to these examples.

[배합실시예]Formulation Example

표 1에 나타낸 배합실시예는 본 발명의 셀룰로오스계 섬유용 표백증진제로서 얻은 것이다. 비교 배합실시예 1에서는, 디에틸렌트리아민 펜타아세트산과 D-소르비톨을 50 : 50(중량비)으로 배합하여 제조하였다.The blending example shown in Table 1 was obtained as a bleaching enhancer for cellulose fibers of the present invention. In Comparative Blending Example 1, diethylenetriamine pentaacetic acid and D-sorbitol were blended at 50:50 (weight ratio) to prepare.

[표 1]TABLE 1

Figure kpo00001
Figure kpo00001

(주) 배합비는 중량부이다.(Note) The blending ratio is parts by weight.

분자량은 VPO법(중기압 침투법)으로 측정된 수평균 분자량으로 표시된다.Molecular weight is represented by the number average molecular weight measured by the VPO method (medium pressure penetration method).

공중합체(1) : 말레산/아크릴산=0.1/1.0(몰비)Copolymer (1): maleic acid / acrylic acid = 0.1 / 1.0 (molar ratio)

공중합체(2) : 말레산/아크릴산=1.0/1.0(몰비)Copolymer (2): maleic acid / acrylic acid = 1.0 / 1.0 (molar ratio)

[실시예 1]Example 1

정련생지 시이팅의 편직물을 본 발명의 표백 증진제를 사용하여 표백하고, 그 표백성을 시험하였다. 그 결과는 표2에 나타내었다.Knitted fabrics of refined dough sheeting were bleached using the bleach enhancer of the present invention and their bleaching properties were tested. The results are shown in Table 2.

표백조건Bleaching conditions

사용수의 경도 25°DHHardness 25 ° DH of use water

욕비(Bath ratio) 1 : 25Bath ratio 1: 25

온도 80℃Temperature 80 ℃

시 간 30분30 minutes

사용약제 표 2 참조Pharmaceuticals See Table 2

평가evaluation

처리된 포(cloth)의 촉감은 관능검사법(functional test method)으로 판정하였다. 백도는 SM 칼라 컴퓨터 모델 SM-3(suga tester 가부시끼가이샤 제)을 사용하여 측정하고, Lab계의 백도식The feel of the treated cloth was determined by a functional test method. Whiteness is measured using a SM color computer model SM-3 (manufactured by suga tester, Kabushiki Kaisha), Lab-based whiteness formula

W=100-((100-L)2+a2+b2)1/2 W = 100-((100-L) 2 + a 2 + b 2 ) 1/2

단, L=측정된 밀도With L = measured density

a=측정된 채도지수a = measured saturation index

b=측정된 채도지수b = measured saturation index

에 준한 백도 W 구하여 평가하였다. 봉제성은 포(cloth)를 4장 겹쳐서 본봉(lock stitch)재봉틀로 바늘#11S를 사용하여 30㎝ 플레인 스티칭한 경우에 지사(ground yarn)에 생기는 불연속성의 수를 평가하였다.Whiteness W according to the evaluation was obtained. Sewing performance was evaluated for the number of discontinuities in the ground yarns when 4 sheets of cloth were stacked and 30 cm plain stitched using needle # 11S as a lock stitch sewing machine.

[표 2]TABLE 2

Figure kpo00002
Figure kpo00002

표2로부터 명확한 바와같이, 과산화수소, 수산화나트륨 및 #3 규산나트륨만을 사용하여 표백한 시료(No.1)는 촉감이 딱딱하고 백도와 봉제성이 약하고, 에틸렌디아민 테트라아세트산 또는 비교화합물을 병용하여 표백한 시료(No.2∼4)는 표백성의 개선을 현저하게 나타내고 있지 못하다. 그와는 반대로, 본 발명의 표백증진제를 병용하여 표백한 시료(No.5~12)는 부드러운 촉감을 보이고 백도와 봉제성이 우수하여서 양호한 표백성을 나타내고 있다.As is clear from Table 2, the sample bleached using only hydrogen peroxide, sodium hydroxide and # 3 sodium silicate (No. 1) was hard to touch, weak in whiteness and sewability, and bleached in combination with ethylenediamine tetraacetic acid or a comparative compound. One sample (Nos. 2 to 4) does not show remarkable improvement in bleaching properties. On the contrary, the samples (Nos. 5 to 12) bleached by using the bleach enhancer of the present invention exhibited a soft touch and excellent whiteness and sewability, showing good bleaching properties.

본 발명의 배합품 원료중 하나인 폴리아크릴산 나트륨을 병용하여 표백한 시료(No.3)는 촉감이 부드럽고 백도와 봉제성이 적당하지만 본 발명의 표백증진제의 수준에는 도달하지 못했다.The sample (No. 3) bleached by using sodium polyacrylate, which is one of the raw materials of the blended product of the present invention, was soft in touch and suitable in whiteness and sewability, but did not reach the level of the bleach enhancer of the present invention.

[실시예 2]Example 2

표백조건Bleaching conditions

Fe+++농도 5ppmFe +++ concentration 5 ppm

욕비(bath ratio) 1 : 80Bath ratio 1: 80

온도 80℃Temperature 80 ℃

시간 30분30 minutes

사용약제 표 3참조Drug use table 3

평가evaluation

실시예 1과 같은 방법으로 백도(W)를 구하여 평가하였다. 인열 강도(tear strength)는 엘멘도르프(elmendorf) 인열시험기를 사용하여, 6.5㎝×10㎝의 시험편(보다 긴 방향으로 경사가 있다)의 양끝을 고정시키고 그 중앙부분에 직각으로 2㎝ 절단하고, 잔여 4.5㎝부분을 인열했을때 나타난 최대중량(g)을 3회측정하여, 그의 평균치를 구하고, 미처리된 포의 수치로 그 수치를 나누어 인열강도로 평가하였다.Whiteness W was obtained and evaluated in the same manner as in Example 1. The tear strength is fixed by using an Elmendorf tear tester, fixing both ends of a 6.5 cm × 10 cm test piece (which is inclined in a longer direction) and cutting 2 cm at a right angle to the center part thereof. The maximum weight (g) which appeared when tearing the remaining 4.5 cm part was measured three times, and the average value thereof was obtained, and the value was divided by the value of the untreated cloth to evaluate the tear strength.

[표 3]TABLE 3

Figure kpo00003
Figure kpo00003

표 3의 결과로부터 명확한 바와 같이, 과산화수소와 수산화나트륨만을 사용하여 표백한 시료(No.13)는 백도가 약하고 인열강도가 매우 저하되었다. 비교배합예 1, 또 는 디에틸렌트리아민 펜타아세트산, 폴리아크릴산 나트륨 및 글루콘산 나트륨을 병용하여 표백한 시료(No.14)는 표백성의 개선이 충분치 않았다.As is clear from the results in Table 3, the sample (No. 13) bleached using only hydrogen peroxide and sodium hydroxide had a weak whiteness and a very low tear strength. The comparative example 1 or the sample (No. 14) which bleached together using diethylenetriamine pentaacetic acid, sodium polyacrylate, and sodium gluconate did not have enough improvement of bleaching property.

이것에 대하여, 본 발명의 표백증진제를 병용하는 표백한 시료(No.18∼25)는 양호한 표백성을 나타내었다.On the other hand, the bleached sample (No. 18-25) which uses the bleach enhancer of this invention showed favorable bleaching property.

[실시예 3]Example 3

이미 정련 표백한 면직물을 고농도의 철이온 존재하에서 표백하고 포오염성을 평가하였다. 그 결과를 표 4에 나타내었다.The already bleached cotton fabrics were bleached in the presence of high concentrations of iron ions and evaluated for fouling. The results are shown in Table 4.

표백조건Bleaching conditions

Fe+++농도 20ppmFe +++ concentration 20 ppm

욕비(bath ratio) 1 : 80Bath ratio 1: 80

온도 80℃Temperature 80 ℃

시간 30분30 minutes

사용약제 표 4참조Pharmaceutical use table 4

평가evaluation

실시예 2에서와 같은 방법으로 백도(W)와 인열강도를 구하고 표백성을 평가하였다. 이런 경우는 원포(原布)와 비교하였을때 백도가 낮기때문에 포의 오염이 심하다는 것을 나타내주고 있다. 표 4에 나타난 결과로부터 명확한 바와 같이, 과산화수소와 수산화나트륨만을 사용하여 표백한 시료(No.26)는 심하게 오염이 되었고 인열 강도는 크게 저하되었다. 디에틸렌트리아민 펜타아세트산, D-소르비톨, 비교배합예, 공중합체(1)등을 병용하여 표백한 시료(27∼30)는 오염이 개선되지 않았다. 이에 대하여, 본 발명의 표백증진제를 병용하여 표백한 시료(No.31∼38)는 실제로 오염을 방지할 수가 있었고, 원포에 유사한 백도와 인열강도를 나타내었다.In the same manner as in Example 2, whiteness (W) and tear strength were obtained, and bleaching was evaluated. In this case, since the whiteness is low compared to the original cloth, it indicates that the cloth is severely polluted. As is clear from the results shown in Table 4, the sample (No. 26) bleached using only hydrogen peroxide and sodium hydroxide was severely contaminated and tear strength was greatly reduced. The samples (27-30) bleached using diethylenetriamine pentaacetic acid, D-sorbitol, comparative formulation, copolymer (1), etc. together did not improve contamination. On the other hand, the samples (Nos. 31 to 38) bleached by using the bleach enhancer of the present invention were able to actually prevent contamination, and showed similar whiteness and tear strength to the original fabric.

[표 4]TABLE 4

Figure kpo00004
Figure kpo00004

* (주) : 원포의 백도는 93.5이다.* (Note): Wonpo is 93.5.

Claims (3)

셀룰로오스계 섬유에 적당하며, (a) 말레산, 아크릴산 또는 메타크릴산의 중합체나 공중합체 또는 그의 염과, (b-1) 일반식 CH2OH(CHOH)nCH2OH인 사카로오스알코올, (이때 n은 2 내지 6의 정수이다), (b-2) 일반식 CH2OH(CHOH)nCOOH인 알돈산, (이때 n은 2 내지 6의 정수이다), (b-3) 알코올이나 산의 수용성염, 또는 (b-4) 알코올이나 산의 락톤으로 구성되는 것을 특징으로 하는 표백증진제.Suitable for cellulose fibers, (a) polymers or copolymers of maleic acid, acrylic acid or methacrylic acid or salts thereof, and (b-1) saccharose alcohols having the general formula CH 2 OH (CHOH) n CH 2 OH, ( N is an integer of 2 to 6), (b-2) an aldonic acid of the general formula CH 2 OH (CHOH) n COOH, where n is an integer of 2 to 6, (b-3) an alcohol or an acid A bleach enhancer, comprising a water-soluble salt of (b-4) or a lactone of an alcohol or an acid. 제1항에 있어서, 10 내지 90중량%의 (a)와, 90 내지 10중량%의 (b-1), (b-2), (b-3) 또는 (b-4)로 구성되는 것을 특징으로 하는 표백증진제.The composition according to claim 1, comprising 10 to 90% by weight of (a) and 90 to 10% by weight of (b-1), (b-2), (b-3) or (b-4). Characterized by bleach enhancers. 제1항에 있어서, 상기 (a)의 수평균분자량이 300 내지 8,000인 것을 특징으로 하는 표백증진제.The bleach enhancer according to claim 1, wherein the number average molecular weight of (a) is 300 to 8,000.
KR1019860006465A 1985-08-05 1986-08-05 Bleaching improving agent KR910002919B1 (en)

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JP60172073A JPS6232195A (en) 1985-08-05 1985-08-05 Bleaching agent enhancer
JP172073 1985-08-05
JP60-172073 1985-08-06

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DE19935258A1 (en) * 1999-07-27 2001-02-01 Henkel Kgaa Bleaching compositions
DE102005005016A1 (en) * 2005-02-03 2006-08-10 Basf Ag Polymers hydrophobic aminonitrile quats for bleach activation
EP2228426A1 (en) * 2009-03-13 2010-09-15 Rohm and Haas Company Scale-reducing additive for automatic dishwashing systems
CN103492632B (en) * 2012-02-24 2015-07-08 日华化学株式会社 Agent and method for refining and bleaching
CN105625013B (en) * 2016-01-25 2018-02-16 苏州印丝特纺织数码科技有限公司 A kind of polyacrylic hydrogen peroxide stabilizer for being used to weave and preparation method thereof

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US4515597A (en) * 1982-12-10 1985-05-07 Ciba Geigy Corporation Magnesium complexes of oligomeric phosphonic acid esters, a process for their preparation and their use as stabilizers in alkaline, peroxide-containing bleach liquors
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GB8619058D0 (en) 1986-09-17
JPS64502B2 (en) 1989-01-06
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GB2178769B (en) 1989-04-05

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