EP0399706A2 - Method of treating fibrous materials - Google Patents
Method of treating fibrous materials Download PDFInfo
- Publication number
- EP0399706A2 EP0399706A2 EP90305117A EP90305117A EP0399706A2 EP 0399706 A2 EP0399706 A2 EP 0399706A2 EP 90305117 A EP90305117 A EP 90305117A EP 90305117 A EP90305117 A EP 90305117A EP 0399706 A2 EP0399706 A2 EP 0399706A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction product
- denotes
- organopolysiloxane
- composition
- groups
- 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
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
Definitions
- This invention relates to' a method of treating fibrous materials and more specifically to a method of treating textile materials.
- fibrous materials is meant fibres of synthetic or naturally occurring materials, for example wool, cotton, polyester, carbon and blends of these.
- the invention relates to the treatment of the fibres as such as well as to the treatment of fabrics or textiles incorporating the fibres.
- compositions comprising amine-containing silicon compounds for imparting desirable properties, e.g. softness, water repellency, lubricity and crease resistance thereto.
- patent specification 1 491 747 for example provides a composition for treatment of synthetic fibres which comprises 1 part of certain aminosilanes and 1 to 20 parts of certain epoxysiloxanes.
- patent specification 1 296 136 provides a process for the treatment of synthetic organic textile fibres which includes the treatment with a composition comprising either a) a mixture of an aminosiloxane and a polyepoxide, b) a mixture of a liquid epoxysiloxane and a polyamine or c) a mixture of a liquid epoxysiloxane and an aminosiloxane.
- a composition comprising either a) a mixture of an aminosiloxane and a polyepoxide, b) a mixture of a liquid epoxysiloxane and a polyamine or c) a mixture of a liquid epoxysiloxane and an aminosiloxane.
- these materials tend to give a certain amount of yellowing of the treated fibres.
- patent 4 757 121 it is proposed to overcome the yellowing problem when treating synthetic fibre made waddings by using a composition comprising 100 parts by weight of a combination of two organopolysiloxanes composed of from 5 to 95% by weight of an amino-substituted organopolysiloxane, and 95 to 5% by weight of a second amino-substituted organopolysiloxane, which is a reaction product of a liquid amino-substituted organopolysiloxane and a liquid organic epoxy compound, from 1 to 50 parts by weight of an epoxy-containing alkoxy silane and from 1 to 50 parts by weight of a monoepoxy compound.
- an improved treating composition can be made by restricting the amine-containing organosiloxane to those which are prereacted with a monoepoxide.
- a method of treating fibrous materials which comprises the application to fibrous materials of a composition comprising as sole amine-containing organosilicon compound the reaction product of a organopolysiloxane having at least one unit of the general formula and at least one unit having the general formula with one or more monoepoxides, wherein X denotes a monovalent hydrocarbon having up to 8 carbon atoms, R denotes a divalent alkylene group, R' denotes a hydrogen atom or a group of the formula R-Z, wherein Z is NHX, NH 2 , NHRNH 2 or NHRNHX, a has a value of 1 or 2 and b has a value of 2 or 3.
- the organopolysiloxane used in the preparation of the reaction product may be any siloxane polymer having at least 1 unit of the general formula and at least one unit having the general formula Preferably it is a substantially linear polydiorganosiloxane polymer, although small amounts of units which cause branching of the siloxane are possible. Such units, which should not be present in more than 5% of the total number of units, have the general structure
- the substituent X may be any hydrocarbon group having up to 8 carbon atoms, for example alkyl, aryl, alkenyl, alkylaryl and arylalkyl.
- X denotes a lower alkyl group.
- Preferably at least 80% and most preferably substantially all X groups are methyl groups. It is, however, possible that small amounts of other substituents are present on silicon atoms, for example hydroxyl or alkoxy groups.
- the group R is a divalent alkylene group, preferably having up to 8 carbon atoms, most preferably from 3 to 8 carbon atoms. Examples of the R group include dimethylene, propylene, isobutylene and hexylene.
- the groups R may be hydrogen or a group of the formula RZ, wherein Z denotes a primary or secondary amine group or a diamine of the formula NHRNH 2 or NHRNHX.
- a has a value of 1 or 2, which means that the unit may be located in the siloxane chain or may be an end-unit of the siloxane chain.
- Examples of the amine-containing substituent are OSi(CH 3 )(CH 2 ) 3 NH 2 , OSi(CH 3 )CH 2 CH(CH 3 )CH 2 NH 2 , OSi(CH 3 )CH 2 CH(CH 3 )CH 2 NH(CH 2 )- 2 NH 2 , O,Si(CH 3 ) 2 CH 2 CH(CH 3 )CH 2 NH(CH 2 CH 3 ), O,Si(CH 3 ) 2 (CH 2 ) 3 NH(CH 2 ) 3 NH(CH 2 ) 3 NH 2 .
- the other units of the organopolysiloxane are units of the general formula
- b has a value of 2 or 3 and X has the meaning as above.
- the units may be present in the siloxane chain or as endgroups of the chain.
- polydiorganosiloxane having from to 10 to 1000 siloxane units, particularly from 100 to 500 units, most preferably about 400 units are used.
- the viscosity of the polydiorganosiloxane tends to determine the softness which is imparted to the treated materials, the higher the viscosity, the softer the finish. However, for reasons of practicality it is preferred to use those materials which are liquid at room temperature.
- Suitable organopolysiloxanes for the preparation of the reaction product for use in the method of the invention are known in the art and many are commercially available. They can be made by methods known in the art, for example by the condensation of aminofunctional silanes or hydrolysis products thereof with cyclic siloxanes in the presence of endblocking units, for example those provided by hexamethyldisiloxanes.
- Monoepoxides employed in the preparation of the reaction product are organic compounds having one epoxy group.
- epoxy is meant a group composed of oxirane oxygen attached to two vicinal carbon atoms.
- Monoepoxides which are suitable for use in the present invention are those wherein the substituent of the said vicinal carbon atoms are hydrogen, hydrocarbon groups or ether or ester containing hydrocarbon groups.
- one of the carbon atoms has only hydrogen atoms while the other carbon atom has an alkyl group attached to it, which may range from methyl to a linear C 21 alkyl group.
- Most preferred are those monoepoxides wherein the alkyl group has from 1 to 10 carbon atoms, especially from 1 to 4 carbon atoms.
- Suitable monoepoxides are ethylene oxide, propylene oxide, butadiene monoxide, 2,3-epoxy-cyclopentane, substituted olefin oxides, e.g. 2, 3-epoxy-propylbenzene, epoxy alcohols, e.g. glycidol, 2,3-epoxy-cyclopentanol, 3,4-epoxy-6-methylcyclohexylmethane, glycidyl ethers, e.g. phenyl glycidyl ether, butyl glycidyl ether or glycidyl esters, e.g.glycidyl acetate.
- Preferred are those monoepoxides of the general formula wherein n has a value of from 0 to 20, preferably 0 to 8, most preferably 0 to 3.
- the reaction product for use in the method of the invention may be prepared according to known methods.
- the two reagents may be reacted together in the presence of a low molecular weight aliphatic alcohol or in the presence of a catalytic amount of water.
- the reaction can be carried out at room temperature in the presence of such catalyst but is preferably carried out at increased temperatures, for example temperatures of 50 C or more.
- a solvent which may be the alcohol mentioned above or other suitable solvents.
- the amount of monoepoxide used in the reaction should be such that no more than 10% of all amine groups in the organopolysiloxane are retained unreacted in the reaction product.
- two monoepoxide molecules can react with the amine. It is preferred that the majority of the amino groups in the reaction product are tertiary amine groups, although the presence of secondary amine groups to the exclusion of tertiary amine groups is also acceptable.
- the amine groups in the reaction product may thus be tertiary, secondary, a mixture of these, or a mixture of either or both with up to a maximum of 10% primary amine groups.
- reaction product is used in the method of the invention, and not a mere mixture of the polydiorganosiloxane and the monoepoxide.
- Mere mixtures which contain polydiorganosiloxanes having relatively high amounts of primary amine groups are not satisfactory, since they will still display a yellowing of the treated materials. Even a mixture of the two components in the presence of water, e.g. by using an emulsion, is unsatisfactory as the yellowing upon treatment with such mixtures or emulsions is worse than treatment according to the invention.
- no primary amines are retained in the reaction product. Most preferably no secondary amines are present either in the reaction product.
- the method of the invention comprises the application to fibrous materials of a composition comprising as sole amine-containing compound the reaction product as described above.
- This application may be done in any convenient way.
- Application methods which are suitable include padding, dipping and spraying of a composition comprising the reaction product.
- the compositions used may be in any suitable form, e.g. solutions, dispersions or emulsions.
- the dispersions may be in aqueous or solvent based materials while the emulsions are preferably oil-in-water type emulsions.
- emulsions particularly microemulsions according to European patent specification 138 192.
- Compositions which are useful in the method of the invention may comprise other ingredients which are useful in treatment compositions for fibrous materials, e.g. fatty acid softeners. Other ingredients e.g. surfactants in the emulsions are also useful. It is, however, preferred that the composition comprises no amine-containing compounds other than the reaction product.
- the method of the invention is suitable for the treatment of both naturally occurring and synthetic fibres, for example carbon fibres, polyester fibres, cotton fibres and blends of cotton and polyester fibres.
- the application may be done at the stage of making the fibres, at the stage of producing the fabrics or in a special treating step later, for example during laundering of a textile fabric.
- Application may be followed by drying at room temperature or at increased temperatures. After the drying stage a further heat treatment of the fibrous materials is preferred.
- the latter is particularly useful when the textile fabrics are treated at the time of their production.
- the presence of small amounts of primary amine groups on the reaction product will increase the durability of the finish on the fibrous materials, especially when they are subjected to laundering operations.
- Fibrous materials and textiles which are treated according to the method of the invention have an improved softener and lubricity, a pleasant feel and handle, without suffering from yellowing due to the treatment.
- a fibrous material treated according to the method of the invention. Also included are fabrics or textiles incorporating fibres when treated according to the method of the invention.
- reaction product which is believed to have the average formula wherein R' denotes
- a bath was prepared with a 2.77% solution in perchloro ethylene of the reaction product prepared in Examples 1 to 5 in which a piece of polyester cotton (65/35) was treated by padding. The piece was heated to 110° C for 1 minute, followed by 2 minutes at 180° C after treatment. The piece had picked up 0.5% by weight of the reaction product.
- reaction product which is believed to have the average formula wherein R denotes
- a bath was prepared with a 2.77% solution in perchloro ethylene of the reaction product prepared in Examples 6 to 10, in which a piece of polyester cotton (65/35) was treated by padding. The piece was heated to 110° C for 1 minute, followed by 2 minutes at 180°C after treatment. The piece had picked up 0.5% by weight of the reaction product.
- reaction product which is believed to have the average formula wherein R denotes
- a bath was prepared with a 2.77% solution in perchloro ethylene of the reaction product prepared in Examples 16 to 20, in which a piece of polyester cotton (65/35) was treated by padding. The piece was heated to 110° C for 1 minute, followed by heating at 180°C for 2 minutes after treatment. The piece had picked up 0.5% by weight of the reaction product.
- a bath was prepared with a 2.77% solution in perchloro ethylene of the amino containing polydiorganosiloxane used in Examples 11 to 15 on its own, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 0.5% by weight of the siloxane. (Comparative Example 1).
- Comparative Example 2 As in Comparative Example 1, but using a mixture of 1 molar part of the polydiorganosiloxane of Comparative Example 1 with 2 molar parts of propylene oxide, but not reacted. (Comparative Example 2).
- Comparative Example 3 was a piece of untreated polyester cotton (blank) as used in Examples 11 to 15.
- a bath was prepared with a 2.77% solution in perchloro ethylene of the amino containing polydiorganosiloxane used in Examples 16 to 20 on its own, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 0.5% by weight of the siloxane. (Comparative Example 4).
- Comparative Example 5 was a piece of untreated polyester cotton (blank) as used in Examples 16 to 20.
- Comparative Example 6 was a microemulsion of a mixture of the two reactants of Example 21, in the same proportions and with the same concentration, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 1 % by weight of the siloxane.
- Comparative Example 7 was a microemulsion of the amino containing polydiorganosiloxane of Example 21 on its own in the same concentration, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 1 % by weight of the siloxane.
- Comparative Example 8 was a piece of untreated polyester cotton (blank) as used in Example 21.
- Comparative Example 9 was a piece of untreated polyester cotton (blank) as used in Examples 22 and 23.
- Comparative Example 10 was a microemulsion of the amino containing polydiorganosiloxane of Example 22 on its own in the same concentration, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 0.5% by weight of the siloxane.
- Example 11 The whiteness index of Example 11 was measured using a Hunterlab Optical sensor, Model D25M and compared with Comparative Examples 1, 2 and 3. The following results were obtained:
- Example 21 The whiteness index of Example 21 was measured using a Hunteriab Optical sensor, Model D25M and compared with Comparative Examples 6, 7 and 8. The following results were obtained:
- the method according to the invention yields treated materials which have very little yellowing in comparison with materials treated according to the prior art, and have a whiteness index which is very close to that of the untreated material.
Abstract
Description
- This invention relates to' a method of treating fibrous materials and more specifically to a method of treating textile materials.
- With the expression fibrous materials is meant fibres of synthetic or naturally occurring materials, for example wool, cotton, polyester, carbon and blends of these. The invention relates to the treatment of the fibres as such as well as to the treatment of fabrics or textiles incorporating the fibres.
- It is known to treat fibrous materials with compositions comprising amine-containing silicon compounds for imparting desirable properties, e.g. softness, water repellency, lubricity and crease resistance thereto. G.B. patent specification 1 491 747 for example provides a composition for treatment of synthetic fibres which comprises 1 part of certain aminosilanes and 1 to 20 parts of certain epoxysiloxanes. G.B. patent specification 1 296 136 provides a process for the treatment of synthetic organic textile fibres which includes the treatment with a composition comprising either a) a mixture of an aminosiloxane and a polyepoxide, b) a mixture of a liquid epoxysiloxane and a polyamine or c) a mixture of a liquid epoxysiloxane and an aminosiloxane. However, these materials tend to give a certain amount of yellowing of the treated fibres. In U.S. patent 4 757 121 it is proposed to overcome the yellowing problem when treating synthetic fibre made waddings by using a composition comprising 100 parts by weight of a combination of two organopolysiloxanes composed of from 5 to 95% by weight of an amino-substituted organopolysiloxane, and 95 to 5% by weight of a second amino-substituted organopolysiloxane, which is a reaction product of a liquid amino-substituted organopolysiloxane and a liquid organic epoxy compound, from 1 to 50 parts by weight of an epoxy-containing alkoxy silane and from 1 to 50 parts by weight of a monoepoxy compound.
- We have found that an improved treating composition can be made by restricting the amine-containing organosiloxane to those which are prereacted with a monoepoxide.
- According to the invention there is provided a method of treating fibrous materials, which comprises the application to fibrous materials of a composition comprising as sole amine-containing organosilicon compound the reaction product of a organopolysiloxane having at least one unit of the general formula
- The organopolysiloxane used in the preparation of the reaction product may be any siloxane polymer having at least 1 unit of the general formula
- The substituent X may be any hydrocarbon group having up to 8 carbon atoms, for example alkyl, aryl, alkenyl, alkylaryl and arylalkyl. Preferably X denotes a lower alkyl group. Preferably at least 80% and most preferably substantially all X groups are methyl groups. It is, however, possible that small amounts of other substituents are present on silicon atoms, for example hydroxyl or alkoxy groups. The group R is a divalent alkylene group, preferably having up to 8 carbon atoms, most preferably from 3 to 8 carbon atoms. Examples of the R group include dimethylene, propylene, isobutylene and hexylene. The groups R may be hydrogen or a group of the formula RZ, wherein Z denotes a primary or secondary amine group or a diamine of the formula NHRNH2 or NHRNHX. a has a value of 1 or 2, which means that the unit may be located in the siloxane chain or may be an end-unit of the siloxane chain. Examples of the amine-containing substituent are OSi(CH3)(CH2)3NH2, OSi(CH3)CH2CH(CH3)CH2NH2, OSi(CH3)CH2CH(CH3)CH2NH(CH2)-2NH2, O,Si(CH3)2CH2CH(CH3)CH2NH(CH2CH3), O,Si(CH3)2(CH2)3NH(CH2)3NH(CH2)3NH2. The other units of the organopolysiloxane are units of the general formula
- wherein b has a value of 2 or 3 and X has the meaning as above. This means that the units may be present in the siloxane chain or as endgroups of the chain. It is preferred that polydiorganosiloxane having from to 10 to 1000 siloxane units, particularly from 100 to 500 units, most preferably about 400 units are used. The viscosity of the polydiorganosiloxane tends to determine the softness which is imparted to the treated materials, the higher the viscosity, the softer the finish. However, for reasons of practicality it is preferred to use those materials which are liquid at room temperature. It is also preferred that from 0.1 to 20 mole% of all siloxane units are units of the formula
- Monoepoxides employed in the preparation of the reaction product are organic compounds having one epoxy group. By the term epoxy is meant a group composed of oxirane oxygen attached to two vicinal carbon atoms. Monoepoxides which are suitable for use in the present invention are those wherein the substituent of the said vicinal carbon atoms are hydrogen, hydrocarbon groups or ether or ester containing hydrocarbon groups. Preferably one of the carbon atoms has only hydrogen atoms while the other carbon atom has an alkyl group attached to it, which may range from methyl to a linear C21 alkyl group. Most preferred are those monoepoxides wherein the alkyl group has from 1 to 10 carbon atoms, especially from 1 to 4 carbon atoms. Examples of suitable monoepoxides are ethylene oxide, propylene oxide, butadiene monoxide, 2,3-epoxy-cyclopentane, substituted olefin oxides, e.g. 2, 3-epoxy-propylbenzene, epoxy alcohols, e.g. glycidol, 2,3-epoxy-cyclopentanol, 3,4-epoxy-6-methylcyclohexylmethane, glycidyl ethers, e.g. phenyl glycidyl ether, butyl glycidyl ether or glycidyl esters, e.g.glycidyl acetate. Preferred are those monoepoxides of the general formula
- The reaction product for use in the method of the invention may be prepared according to known methods. For example, the two reagents may be reacted together in the presence of a low molecular weight aliphatic alcohol or in the presence of a catalytic amount of water. The reaction can be carried out at room temperature in the presence of such catalyst but is preferably carried out at increased temperatures, for example temperatures of 50 C or more. In order to make the reaction more easily handled it may be carried out in the presence of a solvent, which may be the alcohol mentioned above or other suitable solvents. The amount of monoepoxide used in the reaction should be such that no more than 10% of all amine groups in the organopolysiloxane are retained unreacted in the reaction product. Where a primary amine group was present in the organopolysiloxane two monoepoxide molecules can react with the amine. It is preferred that the majority of the amino groups in the reaction product are tertiary amine groups, although the presence of secondary amine groups to the exclusion of tertiary amine groups is also acceptable. The amine groups in the reaction product may thus be tertiary, secondary, a mixture of these, or a mixture of either or both with up to a maximum of 10% primary amine groups.
- It is important that the reaction product is used in the method of the invention, and not a mere mixture of the polydiorganosiloxane and the monoepoxide. Mere mixtures which contain polydiorganosiloxanes having relatively high amounts of primary amine groups are not satisfactory, since they will still display a yellowing of the treated materials. Even a mixture of the two components in the presence of water, e.g. by using an emulsion, is unsatisfactory as the yellowing upon treatment with such mixtures or emulsions is worse than treatment according to the invention. Preferably no primary amines are retained in the reaction product. Most preferably no secondary amines are present either in the reaction product.
- The method of the invention comprises the application to fibrous materials of a composition comprising as sole amine-containing compound the reaction product as described above. This application may be done in any convenient way. Application methods which are suitable include padding, dipping and spraying of a composition comprising the reaction product. The compositions used may be in any suitable form, e.g. solutions, dispersions or emulsions. The dispersions may be in aqueous or solvent based materials while the emulsions are preferably oil-in-water type emulsions. Especially preferred are emulsions, particularly microemulsions according to European patent specification 138 192. Compositions which are useful in the method of the invention may comprise other ingredients which are useful in treatment compositions for fibrous materials, e.g. fatty acid softeners. Other ingredients e.g. surfactants in the emulsions are also useful. It is, however, preferred that the composition comprises no amine-containing compounds other than the reaction product.
- The method of the invention is suitable for the treatment of both naturally occurring and synthetic fibres, for example carbon fibres, polyester fibres, cotton fibres and blends of cotton and polyester fibres. The application may be done at the stage of making the fibres, at the stage of producing the fabrics or in a special treating step later, for example during laundering of a textile fabric. Application may be followed by drying at room temperature or at increased temperatures. After the drying stage a further heat treatment of the fibrous materials is preferred. The latter is particularly useful when the textile fabrics are treated at the time of their production. The presence of small amounts of primary amine groups on the reaction product will increase the durability of the finish on the fibrous materials, especially when they are subjected to laundering operations. Fibrous materials and textiles which are treated according to the method of the invention have an improved softener and lubricity, a pleasant feel and handle, without suffering from yellowing due to the treatment.
- In a further aspect of the invention there is provided a fibrous material treated according to the method of the invention. Also included are fabrics or textiles incorporating fibres when treated according to the method of the invention.
- There now follow a number of examples illustrating the invention in which all parts are expressed by weight unless otherwise mentioned.
- 1 molar part of a polydiorganosiloxane compound of the average formula
- 1 molar part of a polydiorganosiloxane compound of the average formula
- 1 molar part of a polydiorganosiloxane compound of the average formula
- 1 molar part of a polydiorganosiloxane compound of the average formula
- 1 molar part of a polydiorganosiloxane compound of the average formula
- 1 mole of (CH30)2Si(CH3)CH2CH(CH3)CH2NH(CH2)2NH2 and methanol were added to a reaction vessel. 1.1 mole of 1,2 butyleneoxide were added through a dropping funnel and the mixture was heated under a nitrogen blanket to 50' C which was maintained for 1 hour. The product was stripped under reduced pressure on a rotary evaporator. 1 mole of the product was mixed with 3 moles of water and heated to 110°C to allow condensation of the silanes. After purification hexamethyldisiloxane and cyclic dimethylsiloxane were added together with an alkaline catalyst. The mixture was heated for 5 hours to 140° C and then neutralised. The filtered reaction prdouct had the formula
- A bath was prepared with a 2.77% solution in perchloro ethylene of the amino containing polydiorganosiloxane used in Examples 11 to 15 on its own, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 0.5% by weight of the siloxane. (Comparative Example 1).
- As in Comparative Example 1, but using a mixture of 1 molar part of the polydiorganosiloxane of Comparative Example 1 with 2 molar parts of propylene oxide, but not reacted. (Comparative Example 2).
- Comparative Example 3 was a piece of untreated polyester cotton (blank) as used in Examples 11 to 15.
- A bath was prepared with a 2.77% solution in perchloro ethylene of the amino containing polydiorganosiloxane used in Examples 16 to 20 on its own, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 0.5% by weight of the siloxane. (Comparative Example 4).
- Comparative Example 5 was a piece of untreated polyester cotton (blank) as used in Examples 16 to 20.
- Comparative Example 6 was a microemulsion of a mixture of the two reactants of Example 21, in the same proportions and with the same concentration, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 1 % by weight of the siloxane.
- Comparative Example 7 was a microemulsion of the amino containing polydiorganosiloxane of Example 21 on its own in the same concentration, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 1 % by weight of the siloxane.
- Comparative Example 8 was a piece of untreated polyester cotton (blank) as used in Example 21.
- Comparative Example 9 was a piece of untreated polyester cotton (blank) as used in Examples 22 and 23.
- Comparative Example 10 was a microemulsion of the amino containing polydiorganosiloxane of Example 22 on its own in the same concentration, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 0.5% by weight of the siloxane.
- All comparative treated pieces of polyester-cotton were heated to 110°C for 1 minute followed by 2 minutes at 180 C for Comparative Examples 1 to 8 and 5 minutes at 150 C for Comparative Examples 9 and 10. The treated pieces of polyester cotton of Examples 1 to 23 were compared for'softness and yellowing effect. It was found that the increase in molecular weight of the siloxane polymer used gave also an increase in the softness of the treated material. Within each series of similar molecules the best softness was obtained by those materials where n had a value of 0, 1 or 3.
-
-
-
-
- It can be seen from the results that the method according to the invention yields treated materials which have very little yellowing in comparison with materials treated according to the prior art, and have a whiteness index which is very close to that of the untreated material.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB898911970A GB8911970D0 (en) | 1989-05-24 | 1989-05-24 | Method of treating fibrous materials |
GB8911970 | 1989-05-24 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0399706A2 true EP0399706A2 (en) | 1990-11-28 |
EP0399706A3 EP0399706A3 (en) | 1991-03-20 |
EP0399706B1 EP0399706B1 (en) | 1993-09-01 |
Family
ID=10657290
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19900305117 Expired - Lifetime EP0399706B1 (en) | 1989-05-24 | 1990-05-11 | Method of treating fibrous materials |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0399706B1 (en) |
JP (1) | JP2846058B2 (en) |
CA (1) | CA2016833A1 (en) |
DE (1) | DE69003009T2 (en) |
ES (1) | ES2043277T3 (en) |
GB (1) | GB8911970D0 (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0444828A2 (en) * | 1990-03-01 | 1991-09-04 | Dow Corning Limited | Composition for treating carbon fibre precursors |
DE4117864A1 (en) * | 1991-05-31 | 1992-12-03 | Pfersee Chem Fab | WAITER DISPERSIONS OF POLYSILOXANES |
EP0577039A1 (en) * | 1992-06-29 | 1994-01-05 | OSi Specialties, Inc. | Textile softener having reduced yellowing |
US5399652A (en) * | 1992-04-03 | 1995-03-21 | Wacker-Chemie Gmbh | Crosslinkable composition based on aminosilicone |
EP0692567A1 (en) | 1994-07-14 | 1996-01-17 | Wacker-Chemie GmbH | Amionofunctional organopolysiloxane |
US6136215A (en) * | 1999-09-02 | 2000-10-24 | Dow Corning Corporation | Fiber treatment composition containing amine-, polyol-, amide-functional siloxanes |
US6171515B1 (en) | 1999-09-02 | 2001-01-09 | Dow Corning Corporation | Fiber treatment composition containing amine-, polyol-, functional siloxanes |
US6255429B1 (en) | 1999-09-02 | 2001-07-03 | Dow Corning Corporation | Amine-, polyol-, amide-functional siloxane copolymers and methods for their preparation |
WO2003066007A1 (en) * | 2002-02-05 | 2003-08-14 | Dow Corning Corporation | Hair care compositions containing polysiloxanes |
WO2004014326A1 (en) * | 2002-08-09 | 2004-02-19 | Kao Corporation | Detergent compositions |
WO2004016722A1 (en) * | 2002-08-16 | 2004-02-26 | General Electric Corporation | Liquid laundry compositions comprising silicone additives |
US7790801B2 (en) | 2007-07-24 | 2010-09-07 | Momentive Performance Materials Inc. | Organo-functional silicone in emulsion systems and process for preparing same |
EP2444447A2 (en) | 2010-10-25 | 2012-04-25 | Evonik Goldschmidt GmbH | Polysiloxanes with groups containing nitrogen |
EP2557107A1 (en) | 2011-08-12 | 2013-02-13 | Evonik Goldschmidt GmbH | Method for producing polysiloxanes with groups containing nitrogen |
US9346023B2 (en) | 2012-08-21 | 2016-05-24 | General Electric Company | Flux enhancing agent for improving composite polyamide reverse osmosis membrane performance |
US9499671B2 (en) | 2014-10-15 | 2016-11-22 | Ramani Narayan | Hydrophilic polysiloxane compositions containing carbinol groups |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2590234Y2 (en) * | 1993-11-16 | 1999-02-10 | マリンブルーブロー株式会社 | A hollow fence standing on a flower bed, etc. |
WO2011123737A1 (en) * | 2010-04-01 | 2011-10-06 | The Procter & Gamble Company | Care polymers |
DE102010062676A1 (en) | 2010-12-09 | 2012-06-14 | Evonik Goldschmidt Gmbh | Preparations containing polysiloxanes with nitrogen-containing groups |
KR101640714B1 (en) * | 2015-06-11 | 2016-07-18 | 치 솅 엔터프라이즈 컴퍼니 엘티디. | Ski shoe binding |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4757121A (en) * | 1986-09-19 | 1988-07-12 | Shin-Etsu Chemical Co., Ltd. | Silicone-based softening agent for synthetic fibers |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1547884A (en) * | 1975-08-20 | 1979-06-27 | Nuova San Giorgio Spa | Apparatus for reinserting broken yarn in an open end spinning unit |
JPS6039792A (en) * | 1983-08-12 | 1985-03-01 | 松下電工株式会社 | Dimmer |
JPS6110498A (en) * | 1984-06-25 | 1986-01-17 | 大日本塗料株式会社 | Method of forming relief engraving pattern |
JPS6445466A (en) * | 1987-08-14 | 1989-02-17 | Shinetsu Chemical Co | Textile treating composition |
-
1989
- 1989-05-24 GB GB898911970A patent/GB8911970D0/en active Pending
-
1990
- 1990-05-11 EP EP19900305117 patent/EP0399706B1/en not_active Expired - Lifetime
- 1990-05-11 DE DE1990603009 patent/DE69003009T2/en not_active Expired - Fee Related
- 1990-05-11 ES ES90305117T patent/ES2043277T3/en not_active Expired - Lifetime
- 1990-05-15 CA CA 2016833 patent/CA2016833A1/en not_active Abandoned
- 1990-05-24 JP JP2132750A patent/JP2846058B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4757121A (en) * | 1986-09-19 | 1988-07-12 | Shin-Etsu Chemical Co., Ltd. | Silicone-based softening agent for synthetic fibers |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0444828A2 (en) * | 1990-03-01 | 1991-09-04 | Dow Corning Limited | Composition for treating carbon fibre precursors |
EP0444828A3 (en) * | 1990-03-01 | 1991-11-06 | Dow Corning Limited | Composition for treating carbon fibre precursors |
DE4117864A1 (en) * | 1991-05-31 | 1992-12-03 | Pfersee Chem Fab | WAITER DISPERSIONS OF POLYSILOXANES |
US5403886A (en) * | 1991-05-31 | 1995-04-04 | Ciba-Geigy Corporation | Aqueous dispersions of polysiloxanes |
US5399652A (en) * | 1992-04-03 | 1995-03-21 | Wacker-Chemie Gmbh | Crosslinkable composition based on aminosilicone |
EP0577039A1 (en) * | 1992-06-29 | 1994-01-05 | OSi Specialties, Inc. | Textile softener having reduced yellowing |
EP0692567A1 (en) | 1994-07-14 | 1996-01-17 | Wacker-Chemie GmbH | Amionofunctional organopolysiloxane |
US6136215A (en) * | 1999-09-02 | 2000-10-24 | Dow Corning Corporation | Fiber treatment composition containing amine-, polyol-, amide-functional siloxanes |
US6171515B1 (en) | 1999-09-02 | 2001-01-09 | Dow Corning Corporation | Fiber treatment composition containing amine-, polyol-, functional siloxanes |
US6255429B1 (en) | 1999-09-02 | 2001-07-03 | Dow Corning Corporation | Amine-, polyol-, amide-functional siloxane copolymers and methods for their preparation |
WO2003066007A1 (en) * | 2002-02-05 | 2003-08-14 | Dow Corning Corporation | Hair care compositions containing polysiloxanes |
WO2004014326A1 (en) * | 2002-08-09 | 2004-02-19 | Kao Corporation | Detergent compositions |
US7244697B2 (en) | 2002-08-09 | 2007-07-17 | Kao Corporation | Detergent composition comprising a silicon derivative having a group containing both a hydroxy group and a nitrogen atom |
WO2004016722A1 (en) * | 2002-08-16 | 2004-02-26 | General Electric Corporation | Liquid laundry compositions comprising silicone additives |
US7790801B2 (en) | 2007-07-24 | 2010-09-07 | Momentive Performance Materials Inc. | Organo-functional silicone in emulsion systems and process for preparing same |
EP2444447A2 (en) | 2010-10-25 | 2012-04-25 | Evonik Goldschmidt GmbH | Polysiloxanes with groups containing nitrogen |
DE102010062156A1 (en) | 2010-10-25 | 2012-04-26 | Evonik Goldschmidt Gmbh | Polysiloxanes with nitrogen-containing groups |
EP2557107A1 (en) | 2011-08-12 | 2013-02-13 | Evonik Goldschmidt GmbH | Method for producing polysiloxanes with groups containing nitrogen |
DE102011110100A1 (en) | 2011-08-12 | 2013-02-14 | Evonik Goldschmidt Gmbh | Process for the preparation of polysiloxanes with nitrogen-containing groups |
US9346023B2 (en) | 2012-08-21 | 2016-05-24 | General Electric Company | Flux enhancing agent for improving composite polyamide reverse osmosis membrane performance |
US9914098B2 (en) | 2012-08-21 | 2018-03-13 | General Electric Company | Flux enhancing agent for improving composite polyamide reverse osmosis membrane performance |
US9499671B2 (en) | 2014-10-15 | 2016-11-22 | Ramani Narayan | Hydrophilic polysiloxane compositions containing carbinol groups |
Also Published As
Publication number | Publication date |
---|---|
JPH0351375A (en) | 1991-03-05 |
DE69003009T2 (en) | 1994-01-13 |
JP2846058B2 (en) | 1999-01-13 |
ES2043277T3 (en) | 1993-12-16 |
EP0399706A3 (en) | 1991-03-20 |
EP0399706B1 (en) | 1993-09-01 |
DE69003009D1 (en) | 1993-10-07 |
CA2016833A1 (en) | 1990-11-24 |
GB8911970D0 (en) | 1989-07-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0399706B1 (en) | Method of treating fibrous materials | |
EP0441530B1 (en) | Method of treating fibrous materials | |
US4283519A (en) | Organosilicone terpolymers | |
EP0055606B1 (en) | Amino-functional silicone emulsions | |
US5540952A (en) | Non-yellowing textile softening process in which a composition comprising a polyorganosiloxane is used | |
EP3445822B1 (en) | Amino-organopolysiloxane and preparation method thereof | |
CA1159073A (en) | Silicone polyether copolymers | |
US4757121A (en) | Silicone-based softening agent for synthetic fibers | |
KR100517103B1 (en) | Nitrogen Atom-Containing Polysiloxanes, Their Preparation, and Fiber and Fabric Finishing Agent Compositions | |
US4725635A (en) | Silicone-based synthetic fiber finishing agent | |
JPH0798904B2 (en) | Emulsion composition of novel amino-functional polysiloxane | |
JPH0366429B2 (en) | ||
US5824814A (en) | Process for stabilising siloxane polymers | |
EP0523910B1 (en) | Organosilicon compounds | |
US6072017A (en) | Monoacrylate-polyether treated fiber | |
KR101003798B1 (en) | Hydrophilic amino modified polysiloxane and method for preparing thereof | |
JPS584114B2 (en) | Preparation agent for pre-shrunk wool | |
US6384254B1 (en) | Quaternary ammonium salt-containing polysiloxane, making method, and fiber or fabric treating agent composition | |
JPS6129612B2 (en) | ||
EP0095155B1 (en) | Process for preparing quaternary ammonium-functional silicon compounds, products prepared thereof and use of the same | |
KR100271593B1 (en) | Fiber-processing agent | |
EP0044540B1 (en) | Silicone polymer compositions for treating textile materials, processes for preparing the same, a process for treating textile materials and the coated textile material thus treated |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE ES FR GB IT NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
17P | Request for examination filed |
Effective date: 19901221 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE ES FR GB IT NL |
|
17Q | First examination report despatched |
Effective date: 19930203 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR GB IT NL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19930901 Ref country code: BE Effective date: 19930901 |
|
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI CASETTA & PERANI S.P.A. |
|
REF | Corresponds to: |
Ref document number: 69003009 Country of ref document: DE Date of ref document: 19931007 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2043277 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20000327 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20000330 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20000510 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20000529 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010511 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010512 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20010511 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020301 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030203 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050511 |