Linear random silicone-polyether copolymers with tertiary amino bonds

Abstract

The invention relates to linear random siloxane-polyether copolymers with tertiary amino linkage. The present invention relates to the field of copolymers suitable for use in textiles, and more particularly to copolymers suitable for use in textile end-finished products, such as softeners. More specifically, the present invention relates to linear random copolymers obtained from the polymerization of siloxane monomers, polyglycidyl ether monomers, preferably diglycidyl ether monomers, and secondary amino compounds. The invention also relates to a preparation method of the copolymer and application of the copolymer.

Description

Technical Field

[0001] The present invention relates to the field of copolymers suitable for textiles, and more particularly to copolymers suitable for textile final finishing products such as softeners. More particularly, the present invention relates to linear random copolymers obtained by polymerizing siloxane monomers, polyglycidyl ether monomers (preferably diglycidyl ether monomers) and secondary amino compounds.

[0002] The invention also relates to a method for preparing the copolymer and the use of the copolymer. Background Art

[0003] Household softeners are widely used in daily life to soften clothes during washing. It is known that when cloth garments or towels are washed with such household softeners, good softness is obtained immediately after washing, but this softness fades with its use and is completely lost after the washing operation.

[0004] In the textile industry, softeners are also called textile finishing products and are used at the end of textile manufacturing to provide good softness to textiles. In contrast to household softeners, softeners used in the textile industry must have a lasting softness effect even after multiple washings when applied to textiles in the form of an emulsion. Softeners used as textile finishing products in the textile industry must then exhibit high substantivity. Particularly suitable softeners are polysiloxane polymers terminated with amine groups and especially with quaternary ammonium groups. Polysiloxanes with quaternary ammonium groups used as textile finishing products are widely described in the prior art.

[0005] However, these polysiloxanes are not known to exhibit good hydrophilicity and when applied to textiles they can either reduce the natural hydrophilicity of textiles containing cellulosic fibers or enhance the natural hydrophobicity of textiles containing polyester fibers.

[0006] Therefore, there is a need for a direct polymer suitable for use in textile finishing products that exhibits improved properties of both soft hand and hydrophilicity, regardless of the type of textile treated with such polymer.

[0007] WO 02 / 092904 describes block, non-(AB) nSilicone polyalkylene oxide copolymers, which are used as softeners for textiles and show good softness and hydrophilicity. These copolymers are obtained by the reaction between epoxy-terminated polysiloxane monomers, monoamine compounds and diepoxy-polyalkylene oxide monomers. The monoamine compounds are selected from primary monoamine compounds or combinations of primary and secondary monoamine compounds. WO 02 / 092904 never describes the use of diamine compounds, or even less cyclic diamine compounds, as linkers between two monomers. The copolymers disclosed in WO 02 / 092904 can be in linear form, but can also be crosslinked due to the use of primary monoamines, which can connect twice the monomers involved in the synthesis of the copolymers. Therefore, the form of the polymers obtained in WO 02 / 092904 is not predictable and reproducible at all, because due to the use of primary amines, you can obtain linear copolymers, or crosslinked copolymers, or mixtures of linear and crosslinked copolymers.

[0008] It is known that linear copolymers have different properties than cross-linked copolymers, especially with regard to viscosity. The viscosity depends on the molecular weight of the copolymer, but also on the form of the copolymer, whether it is linear or cross-linked.

[0009] Therefore, there is a need for a polymer suitable for textile final finishing products which has good substantive properties while exhibiting an improved soft hand and which has an acceptable viscosity while maintaining acceptable hydrophilicity, thereby allowing for easier processing by manufacturers.

[0010] There is also a need to have reproducible polymers suitable for textile final finish products which have a linear form and exhibit the above mentioned properties.

[0011] US2012 / 0308494 describes linear polydimethylsiloxane-polyether copolymers with amino and / or quaternary ammonium groups, which are used as softeners for textiles and exhibit good softness and hydrophilicity. The polydimethylsiloxane monomer and the polyether monomer are connected via amino groups such as piperazine. The copolymer according to US2012 / 0308494 is terminated by an amino group different from the amino groups connecting the polydimethylsiloxane monomer and the polyether monomer. Such copolymers exhibit acceptable viscosity.

[0012] These copolymers are obtained by a process that implements several steps and involves a variety of intermediates. However, this method is not easy to implement in all industrial sites because each step and reactor requires several reactors and several operators. This method may cause operator errors and may therefore lead to the production of unsuitable copolymers or copolymers that are inferior to those available on the market.

[0013] There is also a need for a polymer suitable for textile final finishing products which has all the above mentioned properties and which is obtainable by a process which is easy to implement.

[0014] It would therefore be desirable to have a polymer suitable for textile final finishing products which could have good substantive properties and at the same time improve soft hand and hydrophilicity when applied to textiles, while having an acceptable viscosity, in particular below 20000 mPas, making it easier for manufacturers to handle.

[0015] It would also be desirable to have a polymer suitable for textile final finish products whose preparation process is easy to carry out and yields reproducible polymers.

[0016] It is an object of the present invention to provide a polymer which overcomes all or part of the above-mentioned disadvantages.

[0017] Another object of the present invention is to provide a polymer whose preparation can be easily carried out and reproducibly.

[0018] Another object of the present invention is to provide a composition suitable for textiles, comprising said polymer, the application of which to textiles is easy to carry out and at the same time has stability over time.

[0019] Another object of the present invention is to provide a textile treated with the composition or polymer according to the present invention, which simultaneously exhibits excellent hydrophilicity and improved soft hand properties.

[0020] The term "consisting essentially of" followed by one or more characteristics means that in addition to the components or steps explicitly listed, components or steps that do not materially affect the performance and characteristics of the invention may also be included in the methods or materials of the invention.

[0021] The expression "inclusive between X and Y" includes the boundaries unless expressly stated otherwise. This expression means that the target range includes the X and Y values, as well as all values ​​from X to Y.

[0022] Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of the words, such as "include" and "comprising", mean "including but not limited to", and do not exclude other parts, additives, components, integers or steps. In addition, the singular encompasses the plural, unless the context requires otherwise: in particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

[0023] When upper and lower limits are cited for a property (eg, concentration of a component), a range of values ​​defined by the combination of any upper limit with any lower limit may also be implied. Summary of the invention

[0024] The present invention relates to a linear random copolymer obtained by copolymerization of:

[0025] - at least one siloxane monomer comprising at least 2 functional epoxy groups,

[0026] - at least one polyglycidyl ether monomer, preferably a diglycidyl ether monomer, and

[0027] - at least one amine compound comprising at least 2 functional secondary amine groups.

[0028] The invention also relates to a process for preparing a copolymer according to any one of the preceding claims, comprising at least one polymerization step a) in which at least the following substances are contacted in a solvent:

[0029] - a siloxane monomer comprising at least 2 functional epoxy groups,

[0030] - a polyglycidyl ether monomer having 2 to 4 ethylene oxide functional groups, preferably 2 ethylene oxide functional groups, more preferably the polyglycidyl ether monomer is a diglycidyl ether monomer, and

[0031] - Amine compounds comprising at least 2 functional secondary amine groups.

[0032] The present invention further relates to a composition comprising at least one copolymer as described above, wherein the composition is in the form of an emulsion, an aqueous solution or a suspension, preferably in the form of an emulsion.

[0033] Furthermore, the present invention relates to the use of a composition as described above or a copolymer as described above for treating textiles in order to simultaneously improve the soft hand and the hydrophilicity of said textiles.

[0034] The invention also relates to textiles treated with a polymer as described above or with a copolymer as described above.

[0035] The present invention discloses the following scheme:

[0036] Scheme 1. A linear random copolymer obtained by copolymerization of at least one of the following substances:

[0037] - a siloxane monomer comprising at least 2 functional epoxy groups,

[0038] - a polyglycidyl ether monomer, preferably a diglycidyl ether monomer, and

[0039] - Amine compounds comprising at least 2 functional secondary amine groups.

[0040] Scheme 2. The copolymer according to Scheme 1, which is terminated with a terminal secondary amine group.

[0041] Scheme 3. The copolymer according to any one of the preceding schemes, which has a weight percentage of siloxane monomer in the copolymer of 5% to 95%, preferably 65% ​​to 85%, more preferably 70% to 80%.

[0042] Scheme 4. The copolymer according to any one of the preceding schemes, wherein in the copolymer according to the present invention, the mass % of the polyglycidyl ether monomer, preferably the diglycidyl ether monomer, is 5 to 95, preferably 15 to 60, more preferably 18 to 34 by weight.

[0043] Scheme 5. A copolymer according to any one of the preceding schemes, wherein the siloxane monomer has the general formula (I):

[0044]

[0045]

[0046] in:

[0047] R is a C1-C8 alkyl group, preferably a straight-chain C1-C8 alkyl group, more preferably a C1-C3 alkyl group, and even more preferably a methyl group;

[0048] X is a C1-C20 alkyl group, preferably a straight-chain C1-C20 alkyl group, more preferably a straight-chain C1-C4 alkyl group, and even more preferably a n-propyl group;

[0049] Y is a polyalkylene glycol or an

[0050] Y is preferably a linear polyethylene glycol, preferably monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or pentaethylene glycol, and most preferably Y is tetraethylene glycol; m is 30 to 200, preferably 40 to 190; more preferably an integer of 45 to 185.

[0051] Scheme 6. A copolymer according to any one of the preceding schemes, wherein the polyglycidyl ether monomer is a diglycidyl ether monomer having the general formula (II):

[0052]

[0053] in:

[0054] R 1 Selected from -H, C1-C8 alkyl, preferably selected from -H, C1-C8 alkyl, more preferably selected from -H, -OH, C1-C3 alkyl;

[0055] R 2 Selected from -H, C1-C8 alkyl, preferably selected from -H, linear C1-C8 alkyl, more preferably selected from -H, C1-C3 alkyl,

[0056] K is an integer from 1 to 3, more preferably k is 1 or 2;

[0057] n is an integer of 1 to 20, preferably 2 to 15; more preferably 6 to 11.

[0058] Aspect 7. The copolymer according to any one of the preceding aspects, wherein the amine compound is a cyclic or linear amine compound.

[0059] Scheme 8. A copolymer according to any one of the preceding schemes, wherein the amine compound has the general formula (IIIa), (IIIb) or (IIIc):

[0060]

[0061] in

[0062] R 1 To R 6 Independently selected from -H, -Me, Et, Pr, preferably R 1 To R 6 is -H.

[0063] Scheme 9. A method for preparing a copolymer according to any one of the preceding claims, comprising at least one polymerization step a), wherein at least the following substances are contacted in a solvent:

[0064] - a siloxane monomer comprising at least 2 functional epoxy groups,

[0065] - a polyglycidyl ether monomer, preferably a diglycidyl ether monomer, and

[0066] - Amine compounds comprising at least 2 functional secondary amine groups.

[0067] Scheme 10. The method according to Scheme 9, wherein the solvent used in step a) has a boiling point below 100°C, preferably below 90°C, more preferably a boiling point of 70°C to 88°C.

[0068] 11. The process according to any one of the preceding schemes, comprising a step b) of distilling the solvent used in step a).

[0069] Scheme 12. The method according to any one of the preceding schemes, wherein the temperature of the distillation step b) is lower than 100°C, preferably lower than 90°C, more preferably 70°C to 88°C.

[0070] Embodiment 13. The method according to any one of the preceding embodiments, further comprising a step c) of quaternizing the copolymer obtained in step b).

[0071] Scheme 14. The method according to any one of the preceding schemes, wherein the quaternization step c) is a process of introducing an additional methyl group on the N atom after the synthesis of the copolymer, which provides an additional positive charge on the methylated N atom.

[0072] Embodiment 15. A composition comprising at least one copolymer according to any one of Embodiments 1 to 8, wherein the composition is in the form of an emulsion, an aqueous solution or a suspension, preferably an emulsion.

[0073] 16. The composition of claim 15, wherein the copolymer is present in the composition at a concentration of 0.1 wt% to 99.9 wt%, preferably 5 wt% to 40 wt%, more preferably 10 wt% to 30 wt%, and most preferably 11 wt% to 17 wt%, based on the total weight of the composition.

[0074] Embodiment 17. The composition according to any one of embodiments 15 or 16, comprising at least one surfactant.

[0075] Embodiment 18. Use of the composition according to any one of embodiments 15 to 17 or the copolymer according to any one of embodiments 1 to 9 in treating textiles to simultaneously improve the soft hand feel and hydrophilicity of the textiles.

[0076] Embodiment 19. A textile treated with the composition of any one of embodiments 15 to 17 or with the copolymer of any one of embodiments 1 to 8. DETAILED DESCRIPTION

[0077] Linear random copolymer

[0078] The present invention relates to a linear random copolymer obtained by copolymerization of:

[0079] - at least one siloxane monomer comprising at least 2 functional epoxy groups,

[0080] - at least one polyglycidyl ether monomer, preferably a diglycidyl ether monomer, and

[0081] - at least one amine compound comprising at least 2 functional secondary amine groups.

[0082] Specifically, the present invention relates to a linear random copolymer obtained by reacting a siloxane monomer containing at least 2 functional epoxy groups with an amine compound containing at least 2 functional secondary amine groups to obtain a reaction product and further reacting the reaction product with a polyglycidyl ether monomer, preferably a diglycidyl ether monomer.

[0083] A polyglycidyl ether monomer according to the invention is understood to be an ether monomer comprising at least two functional epoxy groups.

[0084] The polyglycidyl ether monomer preferably contains 2 to 4 functional epoxy groups, preferably the polyglycidyl ether monomer is a diglycidyl ether monomer containing 2 functional epoxy groups. If a polyglycidyl ether monomer having more than 2 functional epoxy groups is used, the functional epoxy groups may be partially protected. The amount of reagent required to protect the functional epoxy groups must be selected so that about two unprotected epoxy groups remain in the polyglycidyl ether monomer. For example, the functional epoxy groups can be protected by adding an equimolar amount of diethanolamine, which is a secondary amine and can react with each epoxy group. Deprotection is not possible in this process.

[0085] When the linear random copolymer of the present invention is applied to textiles, it makes it possible to obtain textiles having both improved soft hand feel and improved hydrophilicity.

[0086] "Copolymer" refers to an oligomer or a linear or branched macromolecule having a sequence consisting of several repeating units (or monomer units), wherein at least two units have different chemical structures.

[0087] "Linear" refers to a polymer or copolymer consisting of a single continuous chain of repeating units. The covalently bonded atoms form the backbone of the polymer, which may be optionally substituted with one or more alkyl groups containing less than 10 carbon atoms, preferably containing 1 to 8 carbon atoms, more preferably containing 1 to 4 carbon atoms.

[0088] "Monomeric unit" or "monomer" refers to a molecule that can be converted into an oligomer or macromolecule by combining with itself or with other molecules of the same type. A monomer represents the smallest constitutional unit, which is repeated to produce an oligomer or macromolecule.

[0089] "Random copolymer" refers to an oligomer or macromolecule in which the sequential distribution of monomer units follows a known statistical law. For example, when a copolymer is composed of monomer units distributed as a Markov distribution, the copolymer is considered to be random. The distribution of monomer units in the polymer chain depends on the reactivity of the polymerizable functional groups of the monomers and the relative concentrations of the monomers. The linear random copolymers of the present invention are different from block copolymers and gradient copolymers. "Block" refers to a part of a copolymer that contains several identical or different monomer units, and it has at least one specific feature of composition or configuration, by which it can be distinguished from the adjacent part. Gradient copolymer refers to a copolymer having monomer units of at least two different structures, and its monomer composition gradually changes along the polymer chain, thereby gradually transitioning from one end of the polymer chain rich in one monomer unit to the other end rich in another monomer unit.

[0090] According to the present invention, the terms "copolymer", "random linear copolymer" and "linear copolymer" all refer to the copolymer according to the present invention and can be used interchangeably.

[0091] "Copolymerization" or "polymerization" refers to the process of converting a mixture of at least two monomer units of different chemical structures into an oligomer or copolymer. According to the present invention, the terms "copolymerization" and "polymerization" have the same meaning and are interchangeable.

[0092] In one embodiment, the copolymer according to the present invention is suitable for use in textiles. More preferably, the copolymer according to the present invention is suitable for use in textile final finishing products, such as softeners.

[0093] As used herein, the terms "textile" and "textile material" must be interpreted broadly and can have a very wide range of manifestations, for example in the form of fibers, yarns, fabrics, garments, knitwear, wovens and nonwovens. The copolymers according to the invention are suitable for treating a variety of textile materials. The textile according to the invention can be a textile based on natural (non-synthetic) cellulose, such as cotton, silk, wool, linen and hemp, or a synthetic textile material, such as polyamide, polyurethane, polyacrylic acid, polyester, polyolefin, polylactic acid (polylactide), or also a mixture of natural textile materials with synthetic textile materials, for example a mixture of cotton and polyester fibers or polyamide fibers.

[0094] Advantageously, when applied to textiles, the copolymers of the present invention provide excellent soft hand properties to the textiles and also provide improved hydrophilicity to the textiles.

[0095] More advantageously, the copolymers according to the present invention can be used with all types of textiles, which means that when the copolymers are applied to different textiles, they exhibit improved soft hand and hydrophilicity regardless of the type of textile to which they are applied.

[0096] It is known that cellulose based textiles are hydrophilic in nature, whereas synthetic textile materials such as polyester textiles are hydrophobic in nature.

[0097] The copolymer according to the present invention, in addition to providing an excellent soft hand, has the advantage of not reducing the hydrophilicity of cellulose-based textiles to which it is applied, and also improving the hydrophilicity of synthetic textile materials such as polyester textiles to which it is applied.

[0098] As also used herein, the terms "softener", "textile finishing product" and "textile end finishing products" have the same meaning and can be used interchangeably. According to the present invention, the terms "softener", "textile finishing product" and "textile end finishing product" refer to the copolymer according to the present invention obtained by polymerization of siloxane monomers, polyglycidyl ether monomers, preferably diglycidyl ether monomers and secondary amino compounds, and when applied to textiles, the textiles show improved soft hand and hydrophilicity.

[0099] As used herein, the terms "soft feel" and "softness" refer to the properties of textiles after treatment with the copolymer according to the present invention. The soft feel of textiles treated with the copolymer according to the present invention is a tactile evaluation or hand evaluation. The soft feel of the treated textiles according to the present invention is performed by a hand panel, and the tested textiles are graded from softest to roughest (1 being the softest).

[0100] In one embodiment, the linear random copolymer according to the invention is terminated with terminal secondary amine groups.

[0101] The term "terminated linear random copolymer" or "terminated copolymer" as used in the present invention refers to a copolymer chain according to the present invention that carries a terminal secondary amine group at each end of its chain. The terminal secondary amine group is generated by the reaction between the terminal epoxy group from the siloxane monomer of the copolymer or from the polyglycidyl ether monomer, preferably the diglycidyl ether monomer of the copolymer and the amine compound according to the present invention.

[0102] In a preferred embodiment, the capped terminal amine groups of the copolymers according to the invention are quaternary ammonium groups.

[0103] The copolymer according to the present invention also contains tertiary amino groups. The tertiary amino groups are generated by the reaction between the siloxane monomers from the copolymer or the epoxy groups from the polyglycidyl ether monomers, preferably diglycidyl ether monomers, of the copolymer and the amine compound according to the present invention. In contrast to the terminal secondary amine groups carried at each end of the copolymer, the tertiary amino groups are contained in the linear backbone of the copolymer and link the siloxane monomers and the polyglycidyl ether monomers, preferably diglycidyl ether monomers together.

[0104] In a preferred embodiment, the capped terminal amine groups and the tertiary amino groups of the copolymers according to the invention are in the form of quaternary ammonium groups.

[0105] In one embodiment, the linear random copolymer according to the present invention has a weight percentage of siloxane monomers in the copolymer of 5% to 95%, preferably 65% ​​to 85%, more preferably 70% to 80%.

[0106] In one embodiment, the linear random copolymer according to the present invention has a molar percentage of siloxane monomer in the copolymer of 0.44% to 24%, preferably 5% to 21%, more preferably 10% to 17%.

[0107] In a preferred embodiment, the linear random copolymer according to the present invention has:

[0108] - 0.44% to 24%, preferably 5% to 21%, more preferably 10% to 17% of the molar percentage of siloxane monomers in the copolymer,

[0109] - 46% to 55%, preferably 48% to 53%, more preferably 49% to 52% by mole percentage of the amine compound in the copolymer, and

[0110] - 20 to 50%, preferably 25 to 44%, more preferably 30 to 39% molar percentage of polyglycidyl ether monomers, preferably diglycidyl ether monomers in the copolymer.

[0111] The mole percentage of monomer in the copolymer is a direct result of adjusting the amount of monomer used to synthesize the copolymer.

[0112] Advantageously, the linear random copolymer according to the invention has:

[0113] - 10% to 17% by mole percentage of siloxane monomers in the copolymer,

[0114] - 49% to 52% by mole percentage of the amine compound in the copolymer, and

[0115] - 30% to 39% molar percentage of polyglycidyl ether monomers, preferably diglycidyl ether monomers in the copolymer.

[0116] In one embodiment, the weight percentage of the polyglycidyl ether monomer of the linear random copolymer according to the present invention in the copolymer is 5% to 95%, preferably 15% to 60%, more preferably 18% to 34%.

[0117] In a preferred embodiment, the linear random copolymer of the present invention has:

[0118] - 5% to 95%, preferably 65% ​​to 85%, more preferably 70% to 80% by weight of siloxane monomers in the copolymer,

[0119] - 1% to 10%, preferably 1.5% to 7%, more preferably 2% to 5% by weight of the amine compound in the copolymer, and

[0120] - 5% to 95%, preferably 15% to 60%, more preferably 18% to 34% by weight of polyglycidyl ether monomers in the copolymer.

[0121] In one embodiment, in the copolymer according to the present invention, the mass ratio between the siloxane monomer and the polyglycidyl ether monomer, preferably the diglycidyl ether monomer, is 51 to 97, preferably 60 to 95, more preferably 70 to 90 by weight.

[0122] The mass ratios of the monomers in all aspects of the present disclosure may be adjusted to control the properties of the copolymer as desired.

[0123] For example, the monomers may be present in a mass ratio of 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5 and 99:1 by weight of the siloxane monomer to the polyglycidyl ether monomer, preferably the diglycidyl ether monomer. Notably, the monomers may be present in a mass ratio of 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5 and 99:1 by weight of the siloxane monomer to the polyglycidyl ether monomer, preferably the diglycidyl ether monomer.

[0124] In a preferred embodiment, the copolymers according to the invention result from the copolymerization of:

[0125] - at least one siloxane monomer comprising at least 2 functional epoxy groups,

[0126] - at least one polyglycidyl ether monomer, preferably a diglycidyl ether monomer, comprising at least 2 functional epoxy groups, and

[0127] - at least one amine compound comprising at least 2 functional secondary amine groups,

[0128] The mass ratio of the siloxane monomer to the polyglycidyl ether monomer, preferably the diglycidyl monomer, is 51 to 97 by weight.

[0129] In one embodiment, the linear random copolymer according to the invention has a polydispersity index (PDI) of 1.35 to 1.55; preferably 1.40 to 1.50. The polydispersity index is obtained by size exclusion chromatography measurement using polystyrene calibrants.

[0130] Contrary to common expectations, surprisingly, these low PDI values ​​can be obtained without extensive workup, since the polymers are obtained directly from the raw materials after removal of the solvent without precipitation.

[0131] In one embodiment, the linear random copolymer according to the invention has a number average molecular weight of 10,000 to 22,000 g / mol, preferably 12,000 to 18,000 g / mol.

[0132] The term "number average molecular weight" used throughout the specification refers to the number average molecular weight measured by size exclusion chromatography, in particular by using polystyrene calibrants. The method of measuring by size exclusion chromatography using polystyrene calibrants is described, for example, in the work (Fontanille, M.; Gnanou, Y., Chimie et physico-chimiedes polymeres [Chemistry and physical chemistry of polymers]. 2nd ed.; Dunod: 2010; p546).

[0133] As used herein, unless otherwise indicated, the word "average" refers to a digital mean.

[0134] The copolymer according to the invention has the advantage of having an acceptable viscosity, which enables the manufacturer to easily handle it without any sticking problems.

[0135] In the context of the present invention, "acceptable viscosity" is understood to be a viscosity of less than 25000 mPas, in particular 16000 to 20000 mPas, which allows the operator to handle the copolymer without any sticking problems. A copolymer with an acceptable viscosity according to the invention also refers to an easily processable copolymer, which means that the copolymer according to the invention is easily dissolved in an aqueous solution or dispersed in an emulsion or dispersion for further application on textiles.

[0136] The term "viscosity" refers to the Brookfield viscosity expressed in mPas. The viscosity is measured using a Brookfield viscometer of type 2000. It is measured at 25°C and at a rotation speed of 300 rpm, and is the reading A of the measurement carried out after 30 seconds at 25°C.

[0137] Siloxane monomer

[0138] In one embodiment, the siloxane monomer according to the present invention is a capped epoxysiloxane.

[0139] As used herein, the term "end-capped epoxysilicone" refers to a silicone-containing chain bearing a terminal epoxy group at each end of the chain.

[0140] In one embodiment, the siloxane monomer according to the present invention has the general formula (I):

[0141]

[0142] in:

[0143] R is a C1-C8 alkyl group, preferably a straight-chain C1-C8 alkyl group, more preferably a C1-C3 alkyl group, and even more preferably a methyl group;

[0144] X is a C1-C20 alkyl group, preferably a straight-chain C1-C20 alkyl group, more preferably a straight-chain C1-C5 alkyl group, and even more preferably an n-propyl group.

[0145] Y is polyalkylene glycol or oxygen.

[0146] Y is preferably a linear polyethylene glycol, preferably monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or pentaethylene glycol, most preferably Y is tetraethylene glycol.

[0147] "Ci-Cj alkyl" refers to a saturated straight or branched hydrocarbon chain containing i to j carbon atoms.

[0148] m is an integer of 30 to 200, preferably 40 to 190; more preferably 45 to 185.

[0149] In a particularly preferred embodiment, the siloxanes according to the invention are according to (Ia):

[0150]

[0151] m is an integer of 30 to 300, preferably 50 to 300; more preferably 70 to 290.

[0152] n is an integer of 1 to 8, preferably 1 to 5; more preferably 2 to 4.

[0153] In one embodiment, the siloxane monomer according to the present invention has the general formula (Ib):

[0154]

[0155] wherein m is an integer of 30 to 200, preferably 40 to 190; more preferably 45 to 185.

[0156] "C1-C8 alkyl" refers to a saturated straight or branched hydrocarbon-containing chain containing 1 to 8 carbon atoms. Preferably, the hydrocarbon-containing chain is straight. Preferably, the hydrocarbon-containing chain contains 1 to 3 carbon atoms. Preferably, the C1-C8 alkyl is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl. More preferably, the C1-C11 alkyl is selected from methyl, ethyl and n-propyl. Advantageously, the C1-C8 alkyl is methyl.

[0157] "C1-C20 alkyl" refers to a saturated straight or branched hydrocarbon chain containing 1 to 20 carbon atoms. Preferably, the hydrocarbon chain is straight. Preferably, the hydrocarbon chain contains 1 to 4 carbon atoms. Preferably, the C1-C20 alkyl is selected from methyl, ethyl, n-propyl and n-butyl. More preferably, the C1-C20 alkyl is n-propyl.

[0158] According to one embodiment, the siloxane monomer according to the invention is a mixture of at least two different siloxane monomers of formula (I). Preferably, the siloxane according to the invention is a mixture of two different siloxane monomers of formula (I).

[0159] According to another embodiment, the siloxane monomer according to the invention consists of a single siloxane monomer of formula (I).

[0160] Polyglycidyl ether monomer

[0161] In one embodiment, the polyglycidyl ether monomer according to the present invention is a diglycidyl ether monomer of the general formula (II):

[0162]

[0163] in:

[0164] R 1 Selected from -H, -OH, C1-C8 alkyl, preferably selected from -H, linear C1-C8 alkyl, more preferably selected from -H, C1-C3 alkyl, preferably R is H;

[0165] R 2 is selected from -H, -OH, C1-C8 alkyl, preferably selected from -H, linear C1-C8 alkyl, more preferably selected from -H, C1-C3 alkyl, preferably R is H,

[0166] k is an integer from 1 to 3, more preferably k is 1 or 2;

[0167] n is an integer from 1 to 20, preferably from 2 to 15; more preferably an integer from 6 to 11;

[0168] Preferably, R 1 is selected from -H or -Me,

[0169] R 2 Selected from -H, -Me or,

[0170] k is 1 or 2

[0171] n is between 6 and 11.

[0172] According to a preferred embodiment, the diglycidyl ether monomer of formula (II) according to the present invention is selected from diglycidyl ether monomers of formula (IIa) or (IIb):

[0173]

[0174] in:

[0175] R 1 Selected from -H, C1-C8 alkyl, preferably selected from -H, linear C1-C8 alkyl, more preferably selected from -H, C1-C3 alkyl;

[0176] n is an integer from 1 to 20, preferably from 2 to 15; more preferably from 6 to 11;

[0177] o is an integer from 1 to 20, preferably from 2 to 15; more preferably from 6 to 11; and

[0178] Diglycidyl ether monomers of formula (II), (IIa) or (IIb) are known to those skilled in the art and are commercially available. Particularly suitable diglycidyl ether monomers are available, for example, from Huntsman ( DY 3601 or DY 3602).

[0179] According to one embodiment, the polyglycidyl ether monomer according to the invention is a mixture of at least two different diglycidyl ether monomers of formula (II), in particular two different diglycidyl ether monomers of formula (IIa) or (IIb).

[0180] Preferably, the polyglycidyl ether monomer according to the present invention is a mixture of two different diglycidyl ether monomers of formula (II).

[0181] Advantageously, the polyglycidyl ether monomer according to the invention is a mixture of two different diglycidyl ether monomers of formula (IIa) or (IIb).

[0182] According to another embodiment, the polyglycidyl ether monomer according to the invention consists of a single diglycidyl ether monomer of formula (II).

[0183] Preferably, the polyglycidyl ether monomer according to the present invention consists of a single diglycidyl ether monomer of formula (IIa) or (IIb).

[0184] Amine compounds

[0185] In one embodiment, the amine compound according to the invention comprises at least 2 functional secondary amine groups. Preferably, the amine compound according to the invention comprises 2 functional secondary amine groups. The secondary amine groups of the amine compound according to the invention react with epoxy groups from polyglycidyl ether monomers, preferably diglycidyl ether monomers or from siloxane monomers to form a linear random copolymer according to the invention. The use of an amine compound comprising a functional secondary amine group as a linker between monomers allows advantageously controlling the structure of the copolymer during its polymerization and thus allows obtaining a linear copolymer according to the invention.

[0186] In a preferred embodiment, the amine compound according to the present invention is a cyclic or linear amine compound. Advantageously, the amine compound according to the present invention is a cyclic amine compound.

[0187] In a preferred embodiment, the two functional secondary amine groups of the amine compound according to the invention are part of the backbone of the amine compound.

[0188] Advantageously, the difunctional secondary amine group of the amine compound according to the invention is part of the cyclic backbone of said amine compound.

[0189] In a preferred embodiment, the amine compound according to the present invention is substituted by at least one substituent selected from C1-C8 alkyl, halogen or -OH.

[0190] The term "halogen" as used herein refers to a fluorine atom, a chlorine atom or a bromine atom.

[0191] In one embodiment, the amine compound of the present invention has the general formula (IIIa), (IIIb) or (IIIc):

[0192]

[0193] in

[0194] R 1 To R 6 Independently selected from -H, -Me, Et, Pr, preferably R 1 To R 6 is -H.

[0195]

[0196] Examples of the amine compound of formula (IIIa) are piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,3-dimethylpiperazine, trans-2,3-dimethylpiperazine, 2,6-dimethylpiperazine and homopiperazine.

[0197] An example of an amine compound of formula (IIIb) is 1,3-bis(4-piperidinyl)propane.

[0198] Examples of the amine compound of formula (IIIc) are N,N-dimethyl-1,8-octanediamine, N,N'-dimethyl-1,6-hexanediamine, N,N'-dimethyl-1,3-propylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-diisopropylethylenediamine, N,N-diisopropyl-1,3-propylenediamine, 1,5-bis(methylamino)-3-oxapentane and N,N-bis[3-(methylamino)propyl]methylamine.

[0199] According to one embodiment, the amine compound according to the invention is a mixture of at least two different amine compounds of the formula (IIIa), (IIIb) or (IIIc).

[0200] Preferably, the amine compound according to the invention is a mixture of two different amine compounds of the formula (IIIa), (IIIb) or (IIIc).

[0201] According to another embodiment, the amine compound according to the present invention consists of a single amine compound monomer of formula (IIIa), (IIIb) or (IIIc).

[0202] Process for preparing the copolymer according to the invention

[0203] The invention also relates to a process for preparing the copolymers according to the invention, comprising at least one polymerization step a) in which at least the following substances are contacted in a solvent:

[0204] - a siloxane monomer comprising at least 2 functional epoxy groups,

[0205] - a polyglycidyl ether monomer, preferably a diglycidyl ether monomer, and

[0206] - Amine compounds comprising at least 2 functional secondary amine groups.

[0207] Preferably, in the first step, a siloxane monomer comprising at least 2 functional epoxy groups is reacted with an amine compound comprising at least 2 functional secondary amine groups to obtain a first reaction product, and then the first reaction product is reacted with a polyglycidyl ether monomer, preferably a diglycidyl ether monomer.

[0208] According to a preferred embodiment, the solvent used in step a) has a boiling point below 100°C, preferably below 90°C, more preferably between 70°C and 88°C.

[0209] Preferably, the solvent used in step a) is an alcohol such as isopropanol, or a glycol ether such as diethylene glycol butyl ether, or an ether such as diethyl ether or tetrahydrofuran (THF).

[0210] According to another preferred embodiment, the polymerization step a) is carried out under an inert atmosphere, such as a nitrogen atmosphere.

[0211] In one embodiment, the process further comprises a distillation step b) of the solvent used in step a) to obtain the copolymer according to the invention and as described above. This distillation step allows obtaining a copolymer ready for use without any further purification.

[0212] Preferably, the distillation step b) is carried out at atmospheric pressure.

[0213] As used herein, the term "atmospheric pressure" refers to approximately 1 atm.

[0214] In a preferred embodiment, the distillation step b) is carried out at a temperature at the boiling point of the solvent.

[0215] Advantageously, the temperature of the distillation step b) is below 100° C., preferably below 90° C., more preferably between 70° C. and 88° C. Preferably, the pressure is reduced stepwise to 500 mbar to completely remove the solvent.

[0216] In one embodiment, the process further comprises a quaternization step c) of the copolymer according to the invention obtained in step b).

[0217] Preferably, the quaternization step c) is a process of introducing additional methyl groups on the N atom after the copolymer is synthesized. This process provides additional positive charges on the methylated N atom.

[0218] Through the quaternization step, the hydrophilicity and surface interaction properties of the copolymers are improved.

[0219] In one embodiment, the process further comprises adding a surfactant before the distillation step b) to avoid high viscosity and to improve the handling and processing of the copolymer and its storage properties.

[0220] Composition and use

[0221] The copolymers according to the invention are intended for use as softeners for textiles.

[0222] The invention also relates to a composition comprising at least one copolymer according to the invention. The composition is applied to textiles to provide the textiles with improved soft hand and hydrophilicity.

[0223] In one embodiment, the composition is in the form of an emulsion, an aqueous solution or a suspension, preferably an aqueous emulsion.

[0224] In a preferred embodiment, the copolymer is present in the composition according to the invention in a concentration of 0.1% to 99.9% by weight, preferably 1 to 99% by weight, preferably 5% to 40% by weight, more preferably 10% to 30% by weight, and most preferably 11% to 17% by weight, based on the total weight of the composition. However, it should be understood that all values ​​and ranges between these values ​​and ranges are encompassed by the present invention.

[0225] In one embodiment, the composition according to the invention comprises at least one surfactant.

[0226] The term "surfactant" refers to a substance that reduces the surface tension of a liquid. Typical examples that can be used for application to textiles are anionic or nonionic surfactants, such as fatty alcohol ethoxylates, fatty alcohol alkoxylates, etc., which act as wetting agents and rewetting agents. The nonionic surfactants to which the present invention relates are linear or branched alkoxylated alcohols having a C8-C18 carbon chain and a degree of ethoxylation / propoxylation of 1-12. Anionic surfactants are selected from sulfates, sulfonates, phosphates of linear or branched alkyl chains with or without alkoxy groups.

[0227] Advantageously, the composition according to the invention comprises at least:

[0228] at least one copolymer according to the invention in a concentration of 0.1% to 99.9% by weight, preferably 1% to 99% by weight, preferably 5% to 40% by weight, more preferably 10% to 30% by weight, most preferably 11% to 17% by weight, calculated on the total weight of the composition, and

[0229] - at least one surfactant in a concentration of 0.1 to 10% by weight, preferably 0.5 to 10% by weight, preferably 1 to 9% by weight, more preferably 2.5 to 6% by weight, most preferably 3 to 5% by weight, based on the total weight of the composition

[0230] The "weight percent" of a copolymer or surfactant in a composition (expressed as weight % or wt%) refers to the wt% of the compound used, based on the total weight of the composition, unless otherwise indicated.

[0231] In another embodiment, the composition according to the invention may also contain a mixture of nonionic and / or anionic surfactants, wherein the nonionic surfactant is an alkoxylated alcohol containing a C8-C18 linear or branched carbon chain, and the alkoxy group is an ethoxy and / or propoxy group with 1 to 11 repeating units. The anionic surfactant is preferably selected from carboxylates, sulfates, sulfonates or phosphates of C8 to C18 linear or branched alkyl chains with or without alkoxy groups.

[0232] In a preferred embodiment, the composition according to the invention may further comprise an organic solvent or hydrotrope, preferably having a hydroxyl functionality and selected from C2 to C10 mono- or polyhydric alcohols having 1-3 hydroxyl groups and 0-4 ether bonds, such as butyl diglycol, polyethylene glycol / propylene glycol, diethylene glycol or sodium cumene sulfonate.

[0233] The present invention also relates to a method for treating a textile with a composition according to the invention or a copolymer of formula (I) according to the invention, wherein the composition or copolymer according to the invention is applied to the textile or incorporated into the textile.

[0234] The invention also relates to the use of a composition according to the invention or a copolymer according to the invention for treating textiles in order to simultaneously improve the soft hand and the hydrophilicity of said textiles.

[0235] The invention also relates to textiles treated with a composition according to the invention or a copolymer according to the invention.

[0236] Example

[0237] The following commercial products were used in the given examples:

[0238] - Commercial product 1: Microemulsion of amino-functional polydimethylsiloxane,

[0239] - Commercial product 2: Crude emulsion of amino-functional polydimethylsiloxane

[0240] - Commercial product 3: Microemulsion of amino silicone block copolymer

[0241] - Commercial product 4: Microemulsion of cationic polysiloxane compound

[0242] - Commercial product 5: Microemulsion of hydrophilic polysiloxane compound

[0243] - Commercial product 6: Microemulsion of hydrophobic polysiloxane compound

[0244] -Knittex FEL (reactive crosslinker based on modified dimethylol dihydroxyethylene urea)

[0245] -Knittex CAT.MO (cross-linking catalyst)

[0246] -Marlipal 13 / 70: ethoxylated isotridecyl alcohol (nonionic surfactant based on ethoxylated C13 alcohol)

[0247] -Lutensol TO-6: (nonionic surfactant based on saturated iso-C13-alcohol)

[0248] Preparation of the copolymers according to the invention

[0249] In a 500 ml three-necked flask equipped with a mechanical stirrer, an addition funnel, a thermometer and a reflux cooler, piperazine was added and mixed with isopropanol under a nitrogen atmosphere until all solids dissolved. The siloxane monomer was added with stirring and the reaction mixture was kept at reflux for 1.5 hours. Then, the reaction mixture was cooled to <40°C and epoxy-functionalized ethylene glycol monomer was added while stirring. The resulting mixture was heated to reflux and stirred continuously for another 2 hours under a nitrogen atmosphere. Then, the resulting mixture was cooled to room temperature and isopropanol was removed by distillation (900-200 mbar in 100 minutes) to obtain a copolymer according to the present invention, with a yield of 99.9%. The resulting copolymer can be directly used in the following emulsion without any other purification.

[0250] Table 1. Amounts of copolymers 1 to 3 according to the invention.

[0251]

[0252] 1 Polyoxypropylene glycol diglycidyl ether monomer

[0253] 2 Epoxy terminated polydimethylsiloxane with a molecular weight of 2000 g / mol

[0254] 3 Epoxy terminated polydimethylsiloxane with a molecular weight of 4000 g / mol

[0255] 4 Epoxy terminated polydimethylsiloxane with a molecular weight of 8000 g / mol

[0256] Preparation of emulsions comprising copolymers according to the invention and comparative copolymers

[0257] The emulsion was prepared by the following steps:

[0258] 1. Combine Marlipal (3 g) 13 / 70 and polymer (10-15 g) and homogenize thoroughly at room temperature (mix for 10 minutes)

[0259] 2. Add butyl diglycol (2 g) to the above mixture and fully homogenize at room temperature (mix for 10 minutes)

[0260] 3. Add about 80 grams of water in 7-8 portions within 15 minutes and heat the mixture to 60°C for 60 minutes to obtain the final emulsion. Adjust the pH to 6-6.5 with 0.4 grams of glycolic acid (57%) and add 0.08 grams of preservative below 35°C. SPX".

[0261] The wicking properties of cotton textiles treated with the emulsions according to the invention and the comparative emulsions were evaluated.

[0262] The results are shown in Tables 2 to 7.

[0263] Table 2. Evaluation of wicking and hydrophilicity of 100% cotton textile material (CO shirt) treated with lotions according to the invention and comparative lotions.

[0264]

[0265]

[0266] Table 3. Evaluation of wicking and hydrophilicity of 100% cotton textile materials (CO Shirt & Easy Care) treated with emulsions according to the invention and comparative emulsions.

[0267]

[0268]

[0269] Table 4. Evaluation of wicking and hydrophilicity of 100% cotton textile materials treated with lotions according to the invention and comparative lotions.

[0270]

[0271]

[0272]

[0273]

[0274]

[0275] The wicking properties of polyester textiles treated with the emulsions according to the invention and the comparative emulsions were evaluated.

[0276] The wicking and hydrophilicity of the materials treated with the emulsions according to the invention and the comparative emulsions before and after washing (5 x 40°C) are given in Tables 7 and 8.

[0277] Table 7. Evaluation of wicking and hydrophilicity of 100% polyester textile materials treated with emulsions according to the invention and comparative emulsions.

[0278]

[0279]

[0280]

[0281]

[0282] Evaluation of the hand (softness) of cotton and polyester textiles treated with the emulsions according to the invention and comparative emulsions.

[0283] The softness and hydrophilicity of cotton and polyester materials before and after treatment with the emulsions according to the invention and the comparative emulsions are given in Table 9.

[0284]

[0285]

[0286] Embodiment 2:

[0287] Preparation of the copolymers according to the invention

[0288] In a 500 ml three-necked flask equipped with a mechanical stirrer, an addition funnel, a thermometer and a reflux cooler, 1.5 g of piperazine and 7.5 g of dodecanoic acid were stirred in 25 ml of butyl carbitol until the mixture was homogenized. Then, 125 g of polyether siloxane monomer (in two parts) was added to the mixture. The resulting mixture was heated at 80 ° C and stirred continuously for 6 hours under a nitrogen atmosphere. Then, the resulting mixture was cooled at room temperature to obtain a copolymer according to the present invention in a yield of 100%. The resulting copolymer was directly used in the emulsions described in Tables 10 and 11 below without any other purification.

[0289] Preparation of emulsions comprising copolymers according to the invention and comparative copolymers

[0290] The emulsion was prepared by the following steps:

[0291] 1. Add Lutensol TO-6 (9-12 g) to acidified water containing 0.3-0.5 g 60% acetic acid and homogenize thoroughly (mix for 10 minutes) at room temperature.

[0292] 2. Add butyl diglycol (3 g) to the above mixture and homogenize thoroughly at room temperature (mix for 10 minutes).

[0293] 3. If the hydrophilicity of the formulation needs to be increased, add 12-17 grams of glycerol to the above mixture and homogenize thoroughly (10 minutes at room temperature).

[0294] 4. Add silicone polymer (15-29 g) and heat at 65°C for 1 hour and homogenize the mixture to obtain the final emulsion. After cooling, add water to 100 g.

[0295] Table 10: Amounts of ingredients in the emulsions.

[0296]

[0297]

[0298] Table 11: Formulation ingredients.

[0299]

[0300] Working Example:

[0301] The formulated samples were applied to 100% cotton fabric by padding process using 13-15% of the dyeing agent and the treated fabric was dried at 130°C for 3 minutes.

[0302] Table 12: Water absorbency and wicking height of cotton Pique knits in a wet-on-wet continuous process.

[0303]

[0304]

[0305] Table 13: Water absorbency and wicking height of polyester:cotton (60:40) blends in a wet-on-wet continuous process.

[0306]

[0307] Table 14: Hand feel ratings initially and after 3HL.

[0308]

[0309]

[0310] Table 15: Crockfastness results initially and after 3HL.

[0311]

[0312] Hand feel evaluation:

[0313] Cut sections from dyed unfinished terry towels and cotton knits and polyester / cotton (60:40) single jersey knits, which had been impregnated with an aqueous solution containing 40 gpl of the emulsion produced according to formulations 1 to 12 and acidified with acetic acid, were wet picked up weight percentage on a laboratory padder and subsequently dried at 120-130°C for 3-7 minutes. The hand properties of the test fabrics treated with the emulsions were evaluated. In order to obtain meaningful results, at least 5 judges were evaluated. The results shown above have a softness from 1 to 5, 5 representing the lowest softness and 1 representing the highest softness.

[0314] Hydrophilicity:

[0315] The hydrophilicity shown in Tables 7 and 8 was subsequently evaluated by a water drop test and the water retention on the terry cloth towels was measured by pouring 50 ml of water on the towels and measuring the water displacement and calculating the % of water absorbed by the towels.

[0316] Wicking Height (AATCC Test Method 197):

[0317] With the aid of the sample, the fabric is cut into 25 x 15 cm (warp and weft directions).

[0318] Place a ruler vertically on the back of the elongated dish inside the box so that the ruler touches the bottom. Fill the elongated dish with distilled or deionized water to a depth of 38 ± 2 mm (1.5 ± 0.1 inches). Remove the ruler from the back of the elongated dish. Secure the ruler to the outside of the weighing pan with tape so that the top of the water surface is at the "0" mm mark on the ruler. Use double-sided tape to secure the sample to the top of the box so that the bottom edge just touches the water surface (the same as the "0" mm mark on the ruler) and immediately start the stopwatch or timer.

[0319] Some lightweight woven, knitted or hydrophobic fabrics may float on the water, in which case a small paper clip or clip may be attached to the end of the sample to be immersed in the water. If a paper clip or clip is used, this should be noted in the report. Monitor the rise in the water level. At 10.0 ± 0.1 minutes, measure the distance the water wicks with a ruler. Record the distance in centimeters. Alternative wicking times may be used depending on the desired end use of the fabric. The same wicking time benchmark should be used when comparing results. Repeat the test on two samples of each fabric to minimize error. Take the average of the two readings for the warp and weft yarns as the reported value.

[0320] Spot test:

[0321] Spots on the treated terry cloth towels were tested using a ppm level chlorine solution. Discoloration was assessed on a scale of 1-5, with 5 being no discoloration and 1 being more discoloration.

[0322] Rubbing fastness (AATCC test method 165):

[0323] Instrument used: Friction and wear testing machine

[0324] There are two test methods: wet friction method and dry friction method.

[0325] Dry friction method

[0326] Cut the sample to be tested and the white woven fabric into 2x2 cm. Under controlled conditions, rub the colored test sample on the base of the friction tester with a white test cloth. Each sample is scratched 10 times. The color transferred to the white test cloth is rated by comparison with the AATCC 9-step color transfer scale or the dyeing gray scale, and the grade is assigned.

[0327] Wet friction method

[0328] Cut the sample to be tested and the white woven fabric into 2x2 cm. Use a dropper to wet the white cloth with distilled water. Under controlled conditions, rub the colored test sample on the base of the rubbing tester with the white test cloth. Each sample is scratched 10 times. The color transferred to the white test cloth is rated by comparison with the AATCC 9-step color transfer scale or the dyeing gray scale, and the grade is assigned.

[0329] result :

[0330] Formulations 8, 9 and 12 showed better feel and good absorbency on pique knits. For polyester:cotton blends (60:40), the initial feel of most formulations was better than Rucofin GES M and after 3HL. The wicking height in all formulations was better than the benchmark, so the performance of the present invention is better than Rucofin GES M. These compositions are beneficial for knitted fabric finishing applications. Formulation 3 is suitable for applications where hydrophilicity is not required.

[0331] test:

[0332] -Hand handling character (initial & 5x 40°C) (washing according to ISO 6330 Washprogramm 4G); The handles are evaluated by testers in a panel test. The lower the number, the better. For example, if there are 5 samples, 1 is the best and 5 is the worst rating. The values ​​are added together to give the total value.

[0333] -Rubbing fastness Rubbing fastness according to DIN EN or ISO 105-X12.

[0334] - Wicking test according to DIN 53924 (initial & 5 x 40°C).

[0335] -TEGEWA drop test method Perform TEGEWA drop test (initial & 5x40℃):

[0336] A drop of water is dropped from a fixed height onto the surface of the test sample. The time required for the specular reflection of the water drop to disappear is measured and recorded as the wetting time. Samples taken before drying should be air dried first.

[0337] All samples should reach moisture equilibrium in a standard atmosphere at 21±1℃ and relative humidity of 65±2%.

[0338] The fabric is mounted in hoop guides without wrinkles on the surface, but without distorting the structure of the material.

[0339] A funnel with a pipette is placed above the hoop with the fixed textile and a drop (drop size 0.05 ml ± 10%, drop height: 40 mm) of distilled water (with or without dye) at 21 ± 3 ° C is dropped. Allow to fall on the test sample. The time required for the fabric surface to lose its specular reflectivity due to the fall is measured. The water drop is determined by placing a ring between the observer and a light source (such as a window or a laboratory spotlight) at an angle that allows the specular reflection of light from the flat surface of the water drop to be clearly seen. As the water drop is gradually absorbed, the area of ​​this small mirror gradually decreases and eventually disappears completely, leaving only a dim wet spot. At this point the stopwatch is stopped and the elapsed time is recorded. The test is stopped when the wetting time exceeds 1 minute. 5 readings are taken and the average is taken.

[0340] - Yellowing with temperature (Fixotest) measures the degree of whiteness after exposure to heat (internal method).

[0341] - Whiteness The degree of whiteness is measured according to GANZ.

[0342] -Jet stability; in-house testing.

Claims

1. A linear random copolymer obtained by copolymerization of: - at least one siloxane monomer comprising at least 2 functional epoxy groups, - at least one polyglycidyl ether monomer, preferably a diglycidyl ether monomer, and - at least one amine compound comprising at least 2 functional secondary amine groups.

2. The copolymer according to claim 1, which is end-capped with a terminal secondary amine group.

3. The copolymer according to any one of the preceding claims, having a weight percentage of siloxane monomers in the copolymer of 5% to 95%, preferably 65% ​​to 85%, more preferably 70% to 80%.

4. The copolymer according to any one of the preceding claims, wherein in the copolymer according to the invention the mass % of polyglycidyl ether monomers, preferably diglycidyl ether monomers, is 5 to 95, preferably 15 to 60, more preferably 18 to 34 by weight.

5. The copolymer according to any one of the preceding claims, wherein the siloxane monomer has the general formula (I): in: R is a C1-C8 alkyl group, preferably a straight-chain C1-C8 alkyl group, more preferably a C1-C3 alkyl group, and even more preferably a methyl group; X is a C1-C20 alkyl group, preferably a straight-chain C1-C20 alkyl group, more preferably a straight-chain C1-C4 alkyl group, and even more preferably a n-propyl group; Y is a polyalkylene glycol or an Y is preferably a linear polyethylene glycol, preferably monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or pentaethylene glycol, and most preferably Y is tetraethylene glycol; m is 30 to 200, preferably 40 to 190; more preferably an integer of 45 to 185.

6. The copolymer according to any one of the preceding claims, wherein the polyglycidyl ether monomer is a diglycidyl ether monomer having the general formula (II): in: R 1 Selected from -H, C1-C8 alkyl, preferably selected from -H, C1-C8 alkyl, more preferably selected from -H, -OH, C1-C3 alkyl; R 2 Selected from -H, C1-C8 alkyl, preferably selected from -H, linear C1-C8 alkyl, more preferably selected from -H, C1-C3 alkyl, K is an integer from 1 to 3, more preferably k is 1 or 2; n is an integer of 1 to 20, preferably 2 to 15; more preferably 6 to 11.

7. The copolymer according to any one of the preceding claims, wherein the amine compound is a cyclic or linear amine compound.

8. The copolymer according to any one of the preceding claims, wherein the amine compound has the general formula (IIIa), (IIIb) or (IIIc): in R 1 To R 6 Independently selected from -H, -Me, Et, Pr, preferably R 1 To R 6 is -H.

9. A process for preparing a copolymer according to any one of the preceding claims, comprising at least one polymerization step a) in which at least the following substances are contacted in a solvent: - a siloxane monomer comprising at least 2 functional epoxy groups, - a polyglycidyl ether monomer, preferably a diglycidyl ether monomer, and - Amine compounds comprising at least 2 functional secondary amine groups.

10. The process according to claim 9, wherein the solvent used in step a) has a boiling point below 100°C, preferably below 90°C, more preferably between 70°C and 88°C.

11. The process according to any one of the preceding claims, comprising a distillation step b) of the solvent used in step a).

12. The process according to any one of the preceding claims, wherein the temperature of the distillation step b) is below 100°C, preferably below 90°C, more preferably from 70°C to 88°C.

13. The process according to any one of the preceding claims, further comprising a quaternization step c) of the copolymer obtained in step b).

14. The method according to any one of the preceding claims, wherein the quaternization step c) is a process of introducing additional methyl groups on the N atoms after synthesis of the copolymer, which provides additional positive charges on the methylated N atoms.

15. A composition comprising at least one copolymer according to any one of claims 1 to 8, wherein the composition is in the form of an emulsion, an aqueous solution or a suspension, preferably an emulsion.

16. The composition according to claim 15, wherein the copolymer is present in the composition at a concentration of 0.1 wt% to 99.9 wt%, preferably 5 wt% to 40 wt%, more preferably 10 wt% to 30 wt%, most preferably 11 wt% to 17 wt%, calculated on the total weight of the composition.

17. A composition according to any one of claims 15 or 16, comprising at least one surfactant.

18. Use of the composition according to any one of claims 15 to 17 or the copolymer according to any one of claims 1 to 9 for treating textiles to simultaneously improve the soft hand and hydrophilicity of the textiles.

19. A textile treated with a composition according to any one of claims 15 to 17 or with a copolymer according to any one of claims 1 to 8.

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