CN1308686A - Water/oil repellant composition - Google Patents
Water/oil repellant composition Download PDFInfo
- Publication number
- CN1308686A CN1308686A CN 99808458 CN99808458A CN1308686A CN 1308686 A CN1308686 A CN 1308686A CN 99808458 CN99808458 CN 99808458 CN 99808458 A CN99808458 A CN 99808458A CN 1308686 A CN1308686 A CN 1308686A
- Authority
- CN
- China
- Prior art keywords
- water
- oil
- oil repellant
- microcapsule
- leather
- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The object is to provide a water/oil repellent composition which can simultaneously perform a water/oil treatment and a polishing treatment to leather products such as leather shoes, etc., by using one water/oil repellent composition, and can also exert excellent water/oil repellent effect and excellent polishing effect. It is constituted so that microcapsules, in which a polishing agent is encapsulated, are dispersed in a water/oil repellent agent.
Description
Detailed description of the invention
The present invention relates to water/oil repellant composition, more specifically relate to contain the water/oil repellant composition of microcapsule, be packaged with rumbling compound in the microcapsule.When carrying out WATER REPELLENT, the reagent of refusing water/oil can penetrate leather, brings into play gratifying water repellency and oil repellent to leatherware (as leather etc.) when water/oil repellant composition of the present invention is used for.In addition, after the reagent infiltration of refusing water/oil and further drying, leather surface is polished, can reach good glossiness, i.e. polishing effect with dried cloth.
Prior art
In order to give leatherware with water repellency and oil repellent, the method that usually adopts is that the component of will refuse water/oil (as fluorine resin etc.) is dissolved in the solvent up to now, and gained solution is administered on the leather, is dried to solvent evaporation then.In order further to improve water repellency and the oil repellent that obtains in this class water/oil repellant composition, multiple composition has been proposed.For example, the applicant has proposed a kind ofly to be used to handle leather, Woven fabric and cellulose materials to give their compositions of height water/oil repellant in Japanese patent gazette 2516889, said composition comprises fluorochemicals that (ⅰ) represented by formula RF-Q-A [wherein, Rf represents fluorine-containing aliphatic part, A represents aliphatic part, and Q represents organic group] and (ⅱ) carrier.When this water/oil repellant composition is used to handle leather, not only give leather with competent water/oil repellant, and can also obtain such effect, promptly outward appearance, sense of touch, feel and other the required quality to leather do not have adverse influence.
For to leatherware (as leather shoes etc.) performance polishing effect, multiple rumbling compound has been proposed up to now, as solid wax, cream, emulsion etc.Under the situation of these all conventional rumbling compounds, by they being applied directly on the leather surface and obtaining polishing effect with dried cloth polishing leather surface.
In addition, leatherware is played the special method of refusing water/oily effect and polishing effect simultaneously comprise a kind of method of using two-component composition, this method is promptly used solvent earlier and is refused water/finish product, drying and use cloth to wipe with to wipe away, use then rumbling compound and polishing with dried cloth.In the method, the operation of two steps is absolutely necessary, and the required working hour is long.Therefore, need provide a kind of water/oil repellant formulation products that can carry out step processing.
Water/oil repellant formulation products as carrying out step processing has a kind of product that obtains in the water/oil repellant composition that silicone oil is directly added on the market.Yet can not obtain effect of sufficient from the angle of polishing effect, therefore require further improvement.
An object of the present invention is to solve the problems referred to above of prior art, a kind of water/oil repellant composition is provided, by using a kind of this water/oil repellant composition to carry out water/oil treatment and polished finish simultaneously to leatherware (as leather shoes etc.), and can also produce good water/oily effect and the good polishing effect refused, and need not to handle for a long time.
The inventor has carried out further investigation to realize above-mentioned purpose.As a result, the inventor finds, is dispersed in by the microcapsule that will be packaged with rumbling compound to comprise water/oil repellant reagent as realizing desired result in the water/oil repellant reagent in the water/oil repellant composition of main ingredient.
As mentioned above, water/oil repellant composition of the present invention contains water/oil repellant reagent as main ingredient, and the feature of said composition is evenly dispersed in the water/oil repellant reagent particularly in the microcapsule that are packaged with rumbling compound.
In the present invention, be packed rumbling compound owing to be dispersed in the water/oil repellant reagent, therefore can avoid directly being dispersed in the following shortcoming that is caused in the water/oil repellant reagent by rumbling compound.That is to say that when water/oil repellant reagent penetrated leather, rumbling compound penetrated leather simultaneously, therefore the rumbling compound of capacity can not be administered on the leather surface, thereby can not estimate polishing effect.In addition, rumbling compound penetrates leather with water/oil repellant reagent, has suppressed water/oil repellant.In addition, when the rumbling compound consumption in the composition that adds increases, can be separated.When being separated, again said composition can not be administered on the leatherware equably.
Therefore, there is no particular restriction to be used for the microcapsule that are packaged with rumbling compound of water/oil repellant composition of the present invention, as long as can avoid above-mentioned shortcoming.That is to say that there is no particular restriction to be packaged with the microcapsule of rumbling compound, if the rumbling compound that encapsulates in the microcapsule can be in the contained solvent of water/oil repellant composition wash-out, and the protective membrane of microcapsule is stable in solvent.For example, the protective membrane that constitutes microcapsule better is the polycondensate film that forms by polyreaction, is more preferably the film of polycondensate (as aminoplast(ic) resin etc.).In these films, better be to use the melocol condenses.Can utilize the known encapsulation technology of the public to form the microcapsule that are packaged with rumbling compound.
The rumbling compound that is encapsulated in the microcapsule comprises common rumbling compound, as long as can realize polishing effect, there is no particular restriction.Consider the process of encapsulation, rumbling compound must be oil-soluble.The preferred example of rumbling compound comprises paraffin, silicone oil, wax, natural fat and oil, but is not limited thereto.The common consumption of this rumbling compound is the 50-99% (weight) of microcapsule gross weight.
The shape and size of microcapsule can have various, but better are spheric.Size better is that diameter (external diameter of protective membrane) is common in the scope of 50-2500 micron, better is the 100-1500 micron.When the size of microcapsule is too big, only apply little pressure and will make microcapsules rupture, can unintentionally the material in the capsule be got out.On the other hand, size too hour, film strength is too high, thereby only applies middle pressure and the material in the capsule can not be got out.When the size of microcapsule too greatly or too hour, all can not realize the homodisperse of microcapsule.
The rumbling compound consumption of needs when the consumption of microcapsule in water/oil repellant composition that is packaged with rumbling compound should be able to satisfy the single administration water/oil repellant composition perhaps should be able to guarantee to use to leatherware the rumbling compound of aequum.
In addition, just known to the inventor, the water/oil repellant reagent that is used as main ingredient should be by thickening, so that microcapsule can be dispersed in the water/oil repellant composition.The example of suitable thickening mode comprises and is used in combination dispersion agent, as thickening material etc.The example of suitable thickening comprise be dissolved in the solvent or can be in solvent the swollen polymeric blends, and the mixture that can form false network, the mixture of polyvalent metal and acid alkyl phosphate for example, but be not limited thereto by ionic bonding.
The microcapsule that are packaged with rumbling compound are dispersed in wherein water/oil repellant reagent, and there is no particular restriction, as long as water/oil repellant reagent can be dissolved in solvent, and do not have a negative impact (as fading etc.) in the time of can be on being administered to leather, and can give enough water/oil repellants.The example of suitable water/oil repellant reagent comprises reaction product, perfluor oxyethane polymer of fluorine-containing acrylic copolymer, fluorine-containing alcohol and lipid acid etc.This class water/oil repellant reagent is used with the state that is dissolved in the organic solvent usually.The example of appropriate organic solvent comprises chlorinated hydrocarbon (as tetrachloroethane, trichloroethane etc.), varsol (as isoparaffin etc.), alcohol (as Virahol etc.), ketone (as methyl ethyl ketone etc.), perhaps their mixture.
Water/oil repellant composition of the present invention is except as the water/oil repellant reagent of main ingredient be packaged with the microcapsule of rumbling compound, also can comprise normally used additive if necessary, as tenderizer, antioxidant, nutrient substance, spices, antiseptic-germicide, antimycotic material, deodorizing composition etc.The add-on of these additional activity components and additive can change in relative broad range according to required result.
Water/oil repellant composition of the present invention can be used with several different methods when being used to handle leatherware (as leather shoes etc.) time.For example, below show a kind of preferred approach.At first, water/oil repellant composition is administered on the leatherware surface so that the water/oil repellant component penetrates leather.Use in the operation at this, the available mean for applying for example is a brush etc.Perhaps, better be to use the mean for applying (as sponge etc.) that is fixed on the container top that water/oil repellant composition is housed.As the result of water/oil repellant composition infiltration, leather is endowed good water/oil repellant.In this stage, the rumbling compound microcapsule that contain in nearly all water/oil repellant composition are all stayed on the leather surface.After solvent evaporation or drying, by staving the microcapsule of staying on the leather surface that contain rumbling compound, thereby the rumbling compound of encapsulation is discharged on the leather surface with dried cloth wiping.Simultaneously, with same used in the last operation d/d rumbling compound of dried cloth wiping, give leather surface thus with significant gloss.
The present invention will be described in more detail with reference to following examples.Be appreciated that the invention is not restricted to following
Embodiment.
Embodiment 1
Preparation is packaged with the microcapsule of rumbling compound:
In the reactor of stainless steel, add 215 gram urea-formaldehyde pre-condensation compounds, 71 gram water and 29 gram sodium sulfate, stir these materials.Under vigorous stirring, further add 0.05 gram carboxymethyl cellulose thickener.Then, and adding 104 gram silicone oil (trade(brand)name: " KF96-500 ", by Shinetsu Kagaku Kogyo Co., Ltd. makes) rumbling compound.In this case, stir simultaneously accurately controlled temperature and mixing rate.Add aqueous citric acid solution, the pH value of material in the reactor is adjusted to 6.By filtering to isolate the microcapsule of formation, washing is also further dry.As a result, obtain being roughly the microcapsule that spheric is packaged with silicone oil, its mean diameter is 423 μ m.
The preparation of water/oil repellant composition:
With the Scotchgard that buys
TMWater/oil repellant reagent (by Minnesota Mining andManufacturing Company of St.Paul, Minnesota makes) is as water/oil repellant reagent.This waterproof gel contains fluorine resin, varsol, mineral oil and thickening material as main ingredient.
The microcapsule that are packaged with silicone oil that previous step is made add the waterproof gel that is used for leather that makes, Scotchgard
TMUse the different amounts (1.0,3.0,5.0 and 10.0 weight part) shown in the following table 1, then dispersing and mixing equably.The result obtains transparent amber gel, wherein is dispersed with microcapsule equably.Following table 1 shows the result of visual appraisal preparation stability in preparation process.
The evaluation of water/oil repellant composition:
In order to evaluate the performance of gained water/oil repellant composition, prepare to have the natural ox-hide of smooth surface (30 centimetres of 30 cm x) as the leather sample.The test water/oil repellant composition is administered on the smooth surface of leather sample, notes not staving microcapsule, then with dry about 1 hour of leather sample air.After the viscosity diminishes of leather sample surfaces, stave microcapsule in the time of with this sample part of dried cloth wiping.Use cloth to wipe with wipe away in, leather surface has been endowed gloss.The add-on of microcapsule is depended in the variation of glossy degree (glossiness).
In the present embodiment, the glossmeter micro-TRI-gloss that buys by use (trade(brand)name is made by the Gardener Co.) glossiness of measuring leather surface changes.Accompanying drawing 1 shows the add-on of microcapsule and glossiness changes the relation of (increase that leather sample surfaces glossiness is glossiness under 100 the situation before processing).From this figure as seen, can improve glossiness by the add-on that increases microcapsule.
Comparative example 1
Repeat embodiment 1 described method, different is that silicone oil (trade(brand)name " KF96-10000 ", by Shinetsu Kagaku Kogyo Co., Ltd. makes) is directly sneaked into the waterproof gel Scotchgard that is used for leather
TMIn, homodisperse mixes then, makes comparative sample.The polishing effect of its silicone oil estimates to be better than the polishing effect of the microcapsule that are packaged with silicone oil.Equally in the present embodiment, the add-on of silicone oil is 1.0,3.0,5.0 or 10.0 weight parts.
With with embodiment 1 described identical mode, with the naked eye evaluate silicone oil stability of formulation in this example.The result obtains the result shown in the following table 1.With with embodiment 1 described identical mode, determine silicone oil add-on and the glossiness relation between changing.As a result, obtain the figure shown in the accompanying drawing 1.In this example, add the big variation that more a spot of silicone oil just can be finished glossiness, because used silicone oil has good polishing effect.In addition, even in the situation of embodiment 1, also can obtain identical or better effect by the add-on that increases microcapsule.Table 1
Zero: form transparent amber gel.*: be separated.
| The amount of capsule or silicone oil (weight part) | Embodiment 1 | Comparative example 1 |
| ?1.0 | ?○ | ?○ |
| ?3.0 | ?○ | ?○ |
| ?5.0 | ?○ | ?× |
| ?10.0 | ?○ | ?× |
As mentioned above, according to the present invention,, can carry out water/oil treatment and polished finish simultaneously to leatherware (as leather shoes etc.) by using a kind of water/oil repellant composition.Therefore, not only this processing need not for a long time, and the water/oil repellant effect that obtains and polishing effect can be increased to good level.
Brief description of drawings
Fig. 1 is the graph of a relation between rumbling compound add-on and glossiness change.
Claims (3)
1. water/oil repellant composition, it comprises water/oil repellant reagent as main ingredient, it is characterized in that the microcapsule that are packaged with rumbling compound are dispersed in the described water/oil repellant reagent.
2. water/oil repellant composition as claimed in claim 1, the protective membrane that it is characterized in that encapsulating the described microcapsule of described rumbling compound are the films of the polycondensate that forms by polyreaction.
3. water/oil repellant composition as claimed in claim 1 or 2 is characterized in that described water/oil repellant composition is thickening.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP127395/1998 | 1998-05-11 | ||
| JP12739598A JP3875400B2 (en) | 1998-05-11 | 1998-05-11 | Water and oil repellent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1308686A true CN1308686A (en) | 2001-08-15 |
| CN1161480C CN1161480C (en) | 2004-08-11 |
Family
ID=14958942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998084581A Expired - Fee Related CN1161480C (en) | 1998-05-11 | 1999-05-07 | Water/oil repellant composition |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP3875400B2 (en) |
| CN (1) | CN1161480C (en) |
| AU (1) | AU749005B2 (en) |
| BR (1) | BR9910376A (en) |
| CA (1) | CA2331535C (en) |
| WO (1) | WO1999058728A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3875400B2 (en) * | 1998-05-11 | 2007-01-31 | スリーエム カンパニー | Water and oil repellent composition |
| CN100504641C (en) * | 2004-09-30 | 2009-06-24 | 佳能株式会社 | Image forming apparatus and method of detecting amount of residual developer |
| JP4894315B2 (en) * | 2006-03-17 | 2012-03-14 | 株式会社Ｌｉｘｉｌ | Coating agent and tile |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1316464A (en) * | 1969-08-22 | 1973-05-09 | Kanebo Ltd | Process of treating fibrous articles with microcapsules containing hydrophobic treating agent |
| US3806260A (en) * | 1971-12-14 | 1974-04-23 | Banknote Corp | Mitt |
| AU582346B2 (en) * | 1983-09-13 | 1989-03-23 | Minnesota Mining And Manufacturing Company | Fluorohydrocarbon sulfonamide compounds and use thereof in treatment of leather, textiles and cellusosic materials |
| US5998541A (en) * | 1995-06-14 | 1999-12-07 | Matsushita Electric Industrial Co., Ltd. | Finishing agents and method of using the same |
| JP3875400B2 (en) * | 1998-05-11 | 2007-01-31 | スリーエム カンパニー | Water and oil repellent composition |
-
1998
- 1998-05-11 JP JP12739598A patent/JP3875400B2/en not_active Expired - Fee Related
-
1999
- 1999-05-07 BR BR9910376-1A patent/BR9910376A/en not_active IP Right Cessation
- 1999-05-07 CA CA002331535A patent/CA2331535C/en not_active Expired - Fee Related
- 1999-05-07 AU AU38895/99A patent/AU749005B2/en not_active Ceased
- 1999-05-07 CN CNB998084581A patent/CN1161480C/en not_active Expired - Fee Related
- 1999-05-07 WO PCT/US1999/010035 patent/WO1999058728A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| CA2331535C (en) | 2007-04-24 |
| AU749005B2 (en) | 2002-06-13 |
| CA2331535A1 (en) | 1999-11-18 |
| WO1999058728A1 (en) | 1999-11-18 |
| CN1161480C (en) | 2004-08-11 |
| JP3875400B2 (en) | 2007-01-31 |
| JPH11323317A (en) | 1999-11-26 |
| BR9910376A (en) | 2001-01-30 |
| AU3889599A (en) | 1999-11-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040811 Termination date: 20170507 |