JPH03119187A - Fabric softening composition - Google Patents

Fabric softening composition

Info

Publication number
JPH03119187A
JPH03119187A JP2230456A JP23045690A JPH03119187A JP H03119187 A JPH03119187 A JP H03119187A JP 2230456 A JP2230456 A JP 2230456A JP 23045690 A JP23045690 A JP 23045690A JP H03119187 A JPH03119187 A JP H03119187A
Authority
JP
Japan
Prior art keywords
fabric softening
peptizing
polymer
softening composition
fabric
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
JP2230456A
Other languages
Japanese (ja)
Other versions
JP2635205B2 (en
Inventor
Mansur Sultan Mohammadi
マンサー・サルタン・モハマデイ
Peter Graham Montague
ピーター・グレイアム・モンタギユー
De Pas Johannes Cornelis Van
ヨハンネス・コルネリス・フアン・デ・パス
Edwin Willis
エドウイン・ウイリス
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever NV
Original Assignee
Unilever NV
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
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Application filed by Unilever NV filed Critical Unilever NV
Publication of JPH03119187A publication Critical patent/JPH03119187A/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/217Polyoxyalkyleneglycol ethers with a terminal carboxyl group; Anhydrides, halides or salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • C11D3/0015Softening compositions liquid
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/02Processes in which the treating agent is releasably affixed or incorporated into a dispensing means

Abstract

PURPOSE: To obtain a fabric softening composition which comprises a water-soluble base, at least one or more fabric softening materials and a peptizing polymer, has a lamella vesicle structure dispersed in the water-soluble base, and shows physical stability of fibers and good fluidity. CONSTITUTION: The peptizing polymer having a hydrophilic main chain and at least one or more hydrophobic branched chains and the water-soluble base are added to water while mixing them, where the fabric softening material heated beforehand is added to obtain the fabric softening composition having the lamella vesicle structure dispersed in the water-soluble base. The obtained composition shows excellent stability while hardly causing phase separating when stored. As the softening material, cationic ones are preferable, for example, di-talodimethyl ammonium chloride having a 12-24C hydrocarbyl group or an imidazolynium base softening agent.

Description

【発明の詳細な説明】 本発明は、布柔軟組成物(Ixb目c−soNenin
gcomposi口ons) 、特に1種又はそれ以上
の布柔軟物質と、任意に、連続水性相中に分散されるラ
メラ小滴(Igmc[lxr d+oplclsl構造
を生じるように十分溶解された電解質とを含む布柔軟組
成物に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention provides fabric softening compositions (order Ixb c-soNenin).
gcomposions), in particular a fabric comprising one or more fabric softeners and optionally an electrolyte sufficiently dissolved to produce a lamellar droplet (Igmc[lxr d+oplclsl structure) dispersed in a continuous aqueous phase. TECHNICAL FIELD The present invention relates to soft compositions.

ラメラ小滴は、種々の文献から、中でも例えばH,A、
 Baraes、  ’DelerBats’ 、 C
h、 2. 1nWrlte+(Ed)、  ’Rhe
omelr7  : Industri+1人ppli
cNions   、  J、  Wile7  & 
 5oot、  Lelchvorjh1980から既
に公知である特別な種類の界面活性剤構造である。
Lamellar droplets have been described from various literature, for example H, A,
Baraes, 'DelerBats', C
h, 2. 1nWrlte+(Ed), 'Rhe
omelr7: Industry+1 person ppli
cNions, J., Wile7 &
5oot, a special type of surfactant structure already known from Lelchvorjh 1980.

ラメラ構造を形成する布柔軟組成物は、例えば欧州特許
第303.473号(Albrighl sod Wi
tson)から公知である。この特許出願明細書には、
水性塩基、2つの長鎖アルキル又はアルケニル基を有す
る陽イオン性の布柔軟剤、及び光学的に異方性の球晶組
成物(spherulilic coIIlposit
ion)を形成するための溶解された電解質を含む布柔
軟組成物が記載されている。
Fabric softening compositions forming a lamellar structure are described, for example, in European Patent No. 303.473 (Albrighl sod Wi
tson). This patent application specification includes:
an aqueous base, a cationic fabric softener having two long-chain alkyl or alkenyl groups, and an optically anisotropic spherulitic composition.
Fabric softening compositions are described that include dissolved electrolytes to form ions.

布柔軟剤製品中のラメラ小滴の存在は、例えば光学技術
、種々の流動測定、X線又は中性子回折、及び電子顕微
鏡のような当業者に公知の手段によって検出し得る。
The presence of lamellar droplets in fabric softener products can be detected by means known to those skilled in the art, such as, for example, optical techniques, various flow measurements, X-ray or neutron diffraction, and electron microscopy.

小滴は、タマネギ様形状の同心二榎層の布柔軟物質分子
から成るが、この眉間には閉じ込められた水又は電解質
溶液(水性相)が存在する。このような小滴をほぼ十分
に密閉充填する系は、物理的安定性と有用な流動性との
非常に望ましい組み合わせを提供する。
The droplet consists of two concentric layers of fabric softener molecules in an onion-like shape, with trapped water or electrolyte solution (aqueous phase) between the eyebrows. Such a system that provides near-well hermetic packing of droplets provides a highly desirable combination of physical stability and useful fluidity.

本製品の粘度及び安定性は、小滴が占める液体の容積率
に依っている。概して、分散されたラメラ相(小滴)の
容積率が高いほど、安定性は良い。
The viscosity and stability of the product is dependent on the volume fraction of the liquid occupied by the droplets. Generally, the higher the volume fraction of the dispersed lamellar phase (droplets), the better the stability.

しかしながら、容積率が高いと、その限度内で注ぎ出す
ことが不可能なゲル化製品を生じさせるような粘度の増
大をも引き起こし得る。この問題は解決されつつある。
However, a high volume fraction can also cause an increase in viscosity, resulting in a gelled product that is impossible to pour out within its limits. This problem is being resolved.

容積率が約0.6又はそれ以上である場合、小滴は正に
隣接する(間隙充填する)。これによって、受容可能な
粘度(例えば2.5F11以下、好ましくは21s−’
のずり速度でlPa5完 以下)を有する道理にかなった安全性が得られる。
When the volume fraction is about 0.6 or greater, the droplets are directly adjacent (gap filling). This results in an acceptable viscosity (e.g. 2.5 F11 or less, preferably 21 s-'
Reasonable safety is achieved with a shear rate of less than lPa5.

伝導率測定は、連続相の伝導率と比較した場合、容積率
の有用な測定方法を提供することが公知である。
Conductivity measurements are known to provide a useful measure of volume fraction when compared to the conductivity of the continuous phase.

一方では安定性と粘度との間の間係・において、他方で
は、ラメラ小滴の容積率において複雑にしている要因は
、小滴の凝集度である。凝集が指示された容積率でラメ
ラ小滴間に生じる場合、それに対応する製品の粘度は液
体全体に及ぶ網状構造の形成によって増大する。凝集に
よるラメラ小滴の変形によりそれらはさらに効率的に充
填されるため、凝集はまた、不安定性も生起し得る。従
って、間隙充填機構による安定化のためにはさらに多く
のラメラ小滴が必要となるが、これは再び粘度増大を引
き起こす。
A complicating factor in the relationship between stability and viscosity, on the one hand, and in the volume fraction of lamellar droplets, on the other hand, is the degree of droplet cohesion. If agglomeration occurs between the lamellar droplets at the indicated volume fraction, the viscosity of the corresponding product increases due to the formation of a network throughout the liquid. Agglomeration can also cause instability, since the deformation of lamellar droplets by aggregation causes them to fill more efficiently. Therefore, more lamellar droplets are required for stabilization by the gap filling mechanism, which again causes an increase in viscosity.

小滴の容積率は柔軟剤濃度を増することによって増大す
るし、また電解質レベルを増することによって減少し得
るが、しかしながら、ラメラ小滴間の凝集は、電解質濃
度のある閾値が、布柔軟物質の指示レベルで(そして任
意の異なる柔軟成分間の固定比率で)交叉する場合に生
じ得る。従って、実際上、上記の効果は、配合可能な布
柔軟物質及び電解質の量に限度はあるが、一方、許容可
能な製品を依然として有することを意味する。原則とし
て、便宜のため及びコスト低減のためには、より高レベ
ルの布柔軟物質が望ましい。また、電解質レベルを上げ
ることは、性能を良くするために用いられるし、あるい
は、時として持ち越し保護(cx+B−owe+ pr
otection)のような二次的利益のために試みら
れることもある。
The volume fraction of the droplets can be increased by increasing the softener concentration and decreased by increasing the electrolyte level; however, agglomeration between lamellar droplets may occur until a certain threshold of electrolyte concentration This can occur if there is a crossover at the indicated level of the material (and at a fixed ratio between any different soft ingredients). In practice, therefore, the above effects mean that there is a limit to the amount of fabric softener and electrolyte that can be incorporated, while still having an acceptable product. In principle, higher levels of fabric softeners are desirable for convenience and cost reduction. Increasing electrolyte levels may also be used to improve performance or sometimes provide carryover protection (cx+B-owe+ pr
It may also be attempted for secondary benefits such as protection.

親水性主鎖と1つ又はそれ以上の疎水性側鎖とから成る
解膠性ポリマーを組成物中に配合することか、柔軟組成
物の容積率に依存する安定性及び/又は粘性に好都合に
作用することを、われわれは見出した。
Incorporation into the composition of a peptizing polymer consisting of a hydrophilic backbone and one or more hydrophobic side chains can advantageously improve stability and/or viscosity depending on the volume fraction of the flexible composition. We found that it works.

従って、本発明は、水性塩基及び1種又はそれ以上の布
柔軟物質を含む布柔軟組成物であって、前記組成物が水
性塩基中に分散されるラメラ小滴構造を有し、前記組成
物が親水性主鎖と1つ又はそれ以上の疎水性側鎖とから
成る解膠性ポリマーをさらに含む組成物に関する。
Accordingly, the present invention provides a fabric softening composition comprising an aqueous base and one or more fabric softening substances, wherein said composition has a lamellar droplet structure dispersed in said composition. further comprising a peptizing polymer comprising a hydrophilic backbone and one or more hydrophobic side chains.

解膠性ポリマーは、所望により、許容可能な粘度を有す
る安定で、容易に分散可能な製品に対する要求に応じ得
るものより多量の柔軟物質及び/又は電解質の配合を可
能にする。さらに、該ポリマーは、(所望により)、従
来、ラメラ分散体が高度に安定性に感受性である或種の
他の成分を、多量に配合することを可能にする。
Peptizing polymers allow for the incorporation of higher amounts of flexibilizer and/or electrolyte, if desired, to meet the need for a stable, easily dispersible product with acceptable viscosity. In addition, the polymer allows (if desired) to incorporate large amounts of certain other components to which lamellar dispersions are traditionally highly sensitive to stability.

本発明は、分散相の容積率が0.5.0.6又はそれ以
上である安定で注ぎ出し可能な製品を処方することを可
能にするが、しかし従来不可能であった成分の組合せ又
は濃度を可能にする。
The present invention makes it possible to formulate stable, pourable products with a volume fraction of the dispersed phase of 0.5, 0.6 or higher, but with combinations of ingredients or Allow concentration.

ラメラ小滴相の容積率は、次の方法で測定してもよい。The volume fraction of the lamellar droplet phase may be measured by the following method.

組成物を、例えば40.0GOGで12時間、遠心分離
して、組成物を透明(連続水性)層、濁りのある富活性
(ラメラ)層、及び(固体又は液体が懸濁されている場
合の)箪二層に分離する。遠心分離の前に、連続水性相
、ラメラ相、及び組成物全体の伝導率を測定する。これ
らからラメラ相の容積率を、^me+1cxa Pb4
sics、 24.636 (1035)に示されてい
るように、B「l1g!eIllHの式を用いて算出又
は概算する。
The composition is centrifuged for 12 hours, e.g. ) Separate into two layers. Prior to centrifugation, the conductivity of the continuous aqueous phase, the lamellar phase, and the entire composition is measured. From these, the volume fraction of the lamellar phase is determined as ^me+1cxa Pb4
sics, 24.636 (1035), using the formula B'l1g!eIllH.

好ましくは、水性連続相の粘度は25mPλS未満、最
も好ましくは15mPss未満、特にlom?s未満で
あって、これらの粘度は毛管粘度計、例えば0slv1
1d粘度計を用いて測定される。
Preferably, the viscosity of the aqueous continuous phase is less than 25 mPλs, most preferably less than 15 mPss, especially lom? s and these viscosities are measured using a capillary viscometer, e.g.
Measured using a 1d viscometer.

製品特性を決定するような実用語において、ポリマーに
関する[解膠性(defloceul*ting) J
という用語は、ポリマーを省いた対応組成物が有意に高
い粘度を有するか及び/又は不安定になることを意味す
る。組成物の粘度は増大するが組成物の安定性は増強し
ないポリマーの使用は容認する意図はない。希釈効果に
よって、即ち連続相の容置に加えることのみによって、
単に粘度を低下させるポリマーを容認する意図もない。
In practical terms such as those that determine product properties, deflocculation J
The term means that the corresponding composition without the polymer has a significantly higher viscosity and/or becomes unstable. There is no intention to condone the use of polymers that increase the viscosity of the composition but do not enhance the stability of the composition. By dilution effect, i.e. only by adding to the container of continuous phase,
There is also no intent to tolerate polymers that merely reduce viscosity.

本発明の範囲内では、比較的高いレベルの解膠性ポリマ
ーを、粘度低下が生じるそれらの系に用いることができ
るけれども、約0.O1重量%〜約2.0重量%の低さ
の一般的レベルは、21s’で、2オーダー以下の大き
さまで粘度を低減し得る。
Within the scope of the present invention, relatively high levels of peptizing polymer can be used in those systems where viscosity reduction occurs, although approximately 0. Typical levels as low as 1 wt.% O to about 2.0 wt.% can reduce viscosity by two orders of magnitude or less at 21s'.

本発明の特に好ましい実施態様は、貯蔵時にほとんど相
分離を示さず、また任意の解膠性ポリマーを含まない対
応組成物より低い粘度を有する。
Particularly preferred embodiments of the invention exhibit little phase separation on storage and have lower viscosities than corresponding compositions that do not contain any peptizing polymer.

本発明の好ましい実施態様は、任意の解膠性ポリマーを
含まない対応組成物より小さい小滴サイズを示す。米国
特許第3.974.076号から、より小さいサイズの
小滴が布柔軟性を増強することは公知であるが、過去に
はこのように小さい小滴は高エネルギー加工によって得
られるだけであった。
Preferred embodiments of the invention exhibit smaller droplet sizes than corresponding compositions that do not include any peptizing polymer. It is known from U.S. Pat. No. 3,974,076 that smaller size droplets enhance fabric flexibility, but in the past such small droplets could only be obtained by high energy processing. Ta.

Claims (1)

【特許請求の範囲】 (1)水性塩基、及び1種又はそれ以上の布柔軟物質を
含む布柔軟組成物であって、前記組成物が水性塩基中に
分散されるラメラ小滴構造を有し、前記組成物が親水性
主鎖と、1つ又はそれ以上の疎水性側鎖とから成る解膠
性ポリマーをさらに含む組成物。 (2)解膠性ポリマーが後記の一般式( I )を有する
請求項1記載の布柔軟組成物。 (3)解膠性ポリマーが後記の一般式(II)を有する請
求項1記載の布柔軟組成物。 (4)解膠性ポリマーが後記の一般式(III)を有する
請求項1記載の布柔軟組成物。 (5)解膠性ポリマーが後記の一般式(IV)を有する請
求項1記載の布柔軟組成物。 (6)組成物の0.1〜2.0重量%の解膠性ポリマー
を含有する請求項1〜5のいずれか一項に記載の布柔軟
組成物。 (7)柔軟剤物質が陽イオン性の布柔軟物質を含む請求
項1〜6のいずれか一項に記載の布柔軟組成物。 (8)20〜60重量%の布柔軟物質を含む請求項1〜
7のいずれか一項に記載の布柔軟組成物。 (9)さらに0.1〜5.0重量%の溶解された電解質
を含む請求項1〜8のいずれか一項に記載の布柔軟組成
物。 (10)pH値が6.0未満である請求項1〜9のいず
れか一項に記載の布柔軟組成物。(11)布柔軟物質を
水性塩基に加える前に解膠性ポリマーを水性塩基中に分
散させることを特徴とする、請求項1〜10の1つ又は
それ以上に記載の布柔軟組成物の製造方法。(12)水
性液中の布柔軟剤物質濃度1〜1,000ppmで請求
項1〜10のいずれか一項に記載の布柔軟組成物を含む
水性液に布を接触させることを包含する布処理方法。 (13)水性塩基と1種又はそれ以上の布柔軟物質とを
含む布柔軟組成物への、親水性主鎖と1つ又はそれ以上
の疎水性側鎖とから成る解膠性ポリマーの使用であって
、前記組成物が、2.5Pas以下の粘度の布柔軟組成
物を製造するための水性塩基中に分散されたラメラ小滴
構造を有することを特徴とする使用。
Claims: (1) A fabric softening composition comprising an aqueous base and one or more fabric softening substances, wherein the composition has a lamellar droplet structure dispersed in the aqueous base. , a composition further comprising a peptizing polymer comprising a hydrophilic backbone and one or more hydrophobic side chains. (2) The fabric softening composition according to claim 1, wherein the peptizing polymer has the following general formula (I). (3) The fabric softening composition according to claim 1, wherein the peptizing polymer has the following general formula (II). (4) The fabric softening composition according to claim 1, wherein the peptizing polymer has the following general formula (III). (5) The fabric softening composition according to claim 1, wherein the peptizing polymer has the following general formula (IV). (6) The fabric softening composition according to any one of claims 1 to 5, containing 0.1 to 2.0% by weight of the composition of a peptizing polymer. (7) The fabric softening composition according to any one of claims 1 to 6, wherein the fabric softening agent comprises a cationic fabric softening substance. (8) Claims 1 to 3 containing 20 to 60% by weight of fabric softening material.
7. The fabric softening composition according to any one of 7. (9) The fabric softening composition of any one of claims 1 to 8 further comprising 0.1 to 5.0% by weight of dissolved electrolyte. (10) The fabric softening composition according to any one of claims 1 to 9, which has a pH value of less than 6.0. (11) Preparation of a fabric softening composition according to one or more of claims 1 to 10, characterized in that the peptizing polymer is dispersed in the aqueous base before adding the fabric softening substance to the aqueous base. Method. (12) Fabric treatment comprising contacting the fabric with an aqueous liquid comprising the fabric softening composition according to any one of claims 1 to 10 at a concentration of fabric softener substance in the aqueous liquid of 1 to 1,000 ppm. Method. (13) Use of a peptizing polymer consisting of a hydrophilic backbone and one or more hydrophobic side chains in a fabric softening composition comprising an aqueous base and one or more fabric softening substances. Use, characterized in that the composition has a lamellar droplet structure dispersed in an aqueous base for producing a fabric softening composition with a viscosity of 2.5 Pas or less.
JP2230456A 1989-08-31 1990-08-31 Fabric softening composition Expired - Fee Related JP2635205B2 (en)

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GB8919669.5 1989-08-31
GB898919669A GB8919669D0 (en) 1989-08-31 1989-08-31 Fabric-softening compositions

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DE (1) DE69017316T3 (en)
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BR9004321A (en) 1991-09-03
ES2071030T3 (en) 1995-06-16
KR910004888A (en) 1991-03-29
GB8919669D0 (en) 1989-10-11
EP0415698A2 (en) 1991-03-06
CA2023950A1 (en) 1991-03-01
DE69017316D1 (en) 1995-04-06
DE69017316T2 (en) 1995-07-20
EP0415698B1 (en) 1995-03-01
KR930007737B1 (en) 1993-08-18
AU6196490A (en) 1991-03-07
CA2023950C (en) 2001-04-17
DE69017316T3 (en) 2004-07-01
EP0415698A3 (en) 1991-04-10
EP0415698B2 (en) 2003-12-03
ES2071030T5 (en) 2004-07-16
AU625206B2 (en) 1992-07-02
JP2635205B2 (en) 1997-07-30
MY106842A (en) 1995-08-30
ZA906971B (en) 1992-05-27

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