linear random silicone-polyether copolymers having tertiary amino linkages

Abstract

This invention relates to the field of copolymers suitable for textiles, and more specifically to copolymers suitable for textile finishing products (such as softeners). More specifically, this invention relates to linear random copolymers derived from the polymerization of organosilicon monomers, polyglycidyl ether monomers (preferably diglycidyl ether monomers), and secondary amine compounds. The invention also relates to methods for preparing said copolymers and the uses of said copolymers.

Description

Technical Field

[0001] This invention relates to the field of copolymers suitable for textiles, and more specifically to copolymers suitable for textile finishing products (such as softeners). More specifically, this invention relates to linear random copolymers derived from the polymerization of organosilicon monomers, polyglycidyl ether monomers (preferably diglycidyl ether monomers), and secondary amine compounds.

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

[0003] Household fabric softener is widely used in daily life to soften clothes during washing. It is known that when washing cloths or towels with this type of fabric softener, good softness is achieved immediately after washing, but this softness diminishes with use and is completely lost after a washing cycle.

[0004] In the textile industry, softeners, also known as textile finishing products, are used in the final stage of textile manufacturing to provide textiles with good softness. Unlike household softeners, softeners used in the textile industry, when applied to textiles in emulsion form, must have a lasting softening effect, even after multiple washes. Therefore, softeners used as textile finishing products in the textile industry must exhibit high fixation. Particularly suitable softeners are polysiloxane polymers end-capped with amine groups, and especially with quaternary ammonium groups. Quaternary ammonium polysiloxanes used as textile finishing products are widely described in the prior art.

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

[0006] Therefore, there is a need for a fixative polymer that is suitable for use in textile finishing products while exhibiting properties that improve softness and hydrophilicity, regardless of the type of textile treated with such a polymer.

[0007] WO 02 / 092904 describes a block non-(AB) with a tertiary amino bond. nOrganosilicon polyalkylene oxide copolymers are used as softeners in textiles and exhibit good softness and hydrophilic properties. These copolymers are obtained through a reaction between an epoxy-terminated polysiloxane monomer, a monoamine compound, and a diepoxy-polyalkylene oxide monomer. The monoamine compound is selected from primary monoamine compounds or combinations of primary and secondary monoamine compounds. WO 02 / 092904 never describes the use of diamine compounds, let alone cyclic diamine compounds as linkers between two monomers. The copolymers disclosed in WO 02 / 092904 can be linear or crosslinked due to the use of a primary monoamine that can link the monomers involved in the synthesis of the copolymer twice. Therefore, the form of the polymer obtained in WO 02 / 092904 is fundamentally unpredictable and unreproducible, as linear copolymers, crosslinked copolymers, or mixtures of linear and crosslinked copolymers can be obtained due to the use of a primary amine.

[0008] It is well known that linear copolymers behave differently from crosslinked copolymers, especially in terms of viscosity. Viscosity depends on the molecular weight of the copolymer, but also on its form—whether it is linear or crosslinked.

[0009] Therefore, there is a need for polymers suitable for textile finishing products that have good adhesion, exhibit improved soft hand feel, maintain acceptable hydrophilicity, and have acceptable viscosity, thus allowing manufacturers to handle them more easily.

[0010] There is also a need for reproducible polymers that have a linear form and exhibit the aforementioned properties, suitable for textile finishing products.

[0011] US 2012 / 0308494 describes linear polydimethylsiloxane-polyether copolymers having amino and / or quaternary ammonium groups, which are used as textile softeners and exhibit good softness and hydrophilic properties. The polydimethylsiloxane monomer and the polyether monomer are linked by amino groups, such as piperazine. The copolymers according to US 2012 / 0308494 are amino-terminated, with the amino group being different from the amino group linking the polydimethylsiloxane monomer and the polyether monomer. Such copolymers exhibit acceptable viscosity.

[0012] These copolymers are obtained through a multi-step process involving various intermediate products. However, this method is difficult to implement in all industrial settings because it requires multiple reactors and multiple operators for each step and reactor. Such a method is prone to operator error and can therefore result in the production of unsuitable copolymers or copolymers with properties inferior to those available on the market.

[0013] Further, there is a need for polymers that possess all the aforementioned properties, are suitable for textile finishing products, and are obtained through easily implemented processes.

[0014] Therefore, there is a desire for polymers suitable for textile finishing products that have good adhesion and can simultaneously improve soft hand feel and hydrophilicity when applied to textiles, while having an acceptable viscosity, especially below 20,000 mPas, thus allowing manufacturers to handle them more easily.

[0015] In addition, it is desirable to have polymers suitable for textile finishing products that exhibit low or no yellowing, are stable to salt, and exhibit low foaming properties.

[0016] It is also desirable to have polymers suitable for use in textile finishing products, whose preparation processes are easy to implement and produce reproducible polymers. In this case, it is particularly desirable to obtain polymers in a short synthesis time and with a simple reaction scheme.

[0017] One object of the present invention is to provide a polymer that overcomes all or some of the aforementioned disadvantages.

[0018] Another object of the present invention is to provide polymers whose preparation process is easy to implement and reproducible.

[0019] Another object of the present invention is to provide a composition containing the said polymer suitable for textiles, which is easy to apply to textiles and stable over time.

[0020] Another object of the present invention is to provide textiles treated with the compositions or polymers according to the present invention that simultaneously exhibit excellent hydrophilic properties and improved soft hand feel properties.

[0021] The term “consistent essentially of” followed by one or more characteristics means that components or steps that do not substantially affect the nature and characteristics of the invention may also be included in the methods or materials of the invention, in addition to those expressly listed.

[0022] The phrase "between X and Y" includes the boundary unless otherwise explicitly stated. This phrase means that the target range includes the values ​​of X and Y, as well as all values ​​from X to Y.

[0023] Throughout this description and claims, the words “comprising” and “containing” and their variations are meant “including, but not limited to”, and do not exclude other structural parts, additives, components, integers, or steps. Furthermore, the singular includes the plural unless the context requires otherwise: specifically, where the indefinite article is used, the description should be understood to consider both the singular and the plural unless the context requires otherwise.

[0024] Where upper and lower limits are cited for properties (such as the concentration of a component), the range of values ​​defined by any combination of upper and lower limits may also be implied. Summary of the Invention

[0025] This invention relates to linear random copolymers derived from at least one copolymer:

[0026] - Organosilicon monomers containing at least two functional epoxy groups,

[0027] - Polyglycidyl ether monomer, preferably diglycidyl ether monomer, and

[0028] - An amine compound containing at least two functional secondary amine groups.

[0029] The present invention also relates to a method for preparing a copolymer according to any one of the preceding claims, the method comprising at least one polymerization step a), wherein at least the following substances are contacted in a solvent:

[0030] - Organosilicon monomers containing at least two functional epoxy groups,

[0031] - A polyglycidyl ether monomer having 2 to 4 ethylene oxide functional groups, preferably 2 ethylene oxide functional groups, and more preferably a diglycidyl ether monomer.

[0032] - An amine compound containing at least two functional secondary amine groups.

[0033] The present invention further relates to compositions comprising at least one copolymer as described above, wherein the composition is in the form of an emulsion, an aqueous diluent or a suspension, preferably in the form of an emulsion.

[0034] Furthermore, the present invention relates to the use of the compositions or copolymers described above in treating textiles to simultaneously improve the softness and hydrophilicity of the textiles.

[0035] The present invention also relates to textiles treated with polymers or copolymers as described above. Detailed Implementation

[0036] Linear random copolymers

[0037] This invention relates to linear random copolymers derived from at least one copolymer:

[0038] - Organosilicon monomers containing at least two functional epoxy groups,

[0039] - Polyglycidyl ether monomer, preferably diglycidyl ether monomer, and

[0040] - An amine compound containing at least two functional secondary amine groups.

[0041] Specifically, the present invention relates to linear random copolymers derived from the reaction of an organosilicon monomer containing at least two functional epoxy groups with an amine compound containing at least two 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.

[0042] What is particularly surprising is that linear random copolymers overcome the aforementioned drawbacks of the prior art and exhibit the described positive properties. In the past, it was thought that such polymers needed to be in the form of block copolymers because different blocks were responsible for different properties, such as the silicone structure moiety responsible for a soft feel and the ether structure moiety responsible for hydrophilic properties. The inventors have now surprisingly discovered that a soft feel and hydrophilic properties can also be obtained through linear random copolymers. Compared to block copolymers, the advantage of linear random copolymers lies in their less complex synthesis, as they require less synthesis time and less complex synthetic methods, such as one-pot reactions.

[0043] The polyglycidyl ether monomer according to the present invention is understood to be an ether monomer containing at least two functional epoxy groups.

[0044] The polyglycidyl ether monomer preferably contains 2 to 4 functional epoxy groups, and more preferably, it is a diglycidyl ether monomer containing 2 functional epoxy groups. If a polyglycidyl ether monomer with more than 2 functional epoxy groups is used, the functional epoxy groups can be partially protected. The amount of reagent required to protect the functional epoxy groups must be selected such that approximately 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, a secondary amine that reacts with each epoxy group. This procedure cannot be used for deprotection.

[0045] When applied to textiles, the linear random copolymer according to the invention makes it possible to obtain textiles that simultaneously have improved softness and improved hydrophilicity.

[0046] Furthermore, the linear random copolymers according to the present invention exhibit very low yellowing, are stable to salt, and exhibit low foaming properties.

[0047] "Copolymer" refers to an oligomer or linear or branched macromolecule having a sequence of multiple repeating units (or monomer units), wherein at least two units have different chemical structures.

[0048] "Linear" means that the polymer or copolymer consists of a single continuous chain of repeating units. Covalently bonded atoms form the backbone of the polymer, which may optionally be replaced by one or more alkyl groups containing fewer than 10 carbon atoms, preferably containing 1 to 8 carbon atoms, more preferably containing 1 to 4 carbon atoms.

[0049] "Monomer unit" or "monomer" refers to a molecule that can be transformed into an oligomer or macromolecule by combining with itself or with other molecules of the same type. A monomer represents the smallest repeating unit that produces an oligomer or macromolecule.

[0050] "Random copolymer" refers to an oligomer or macromolecule in which the sequence distribution of monomer units follows known statistical laws, at least in a portion of the oligomer or macromolecule. For example, when a copolymer is composed of monomer units, it is called a random copolymer, and its distribution follows a Markov distribution. The distribution of monomer units in the polymer chain depends on the reactivity of the polymerizable functional groups of the monomers and the relative concentration of the monomers. The linear random copolymers of the present invention differ from block copolymers and gradient copolymers. "Block" refers to a portion of a copolymer that contains several identical or different monomer units and has at least one specific structural or configurational feature, thereby distinguishing it from adjacent portions, particularly in the whole oligomer or macromolecule. A gradient copolymer refers to a copolymer having at least two different structures of monomer units, whose monomer composition gradually changes along the polymer chain, thus gradually transitioning from one end of the polymer chain rich in one monomer unit to the other end rich in another comonomer.

[0051] According to the present invention, the terms "polymer", "random linear copolymer" and "linear copolymer" all refer to copolymers according to the present invention and are used interchangeably.

[0052] "Copolymerization" or "polymerization" refers to the process of converting a mixture of at least two monomer units with 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.

[0053] In embodiments, the copolymers according to the invention are suitable for textiles. More preferably, the copolymers according to the invention are suitable for textile finishing products, such as softeners.

[0054] As used herein, the terms "textiles" and "textile materials" should be interpreted broadly and can take many forms, such as fibers, yarns, fabrics, garments, knitted fabrics, woven fabrics, and nonwoven fabrics. The copolymers according to the invention are suitable for processing a wide variety of textile materials. Textiles according to the invention can be natural (non-synthetic) cellulose-based textiles such as cotton, silk, wool, flax, and hemp, or synthetic textile materials such as polyamides, polyurethanes, polyacrylates, polyesters, polyolefins, polylactic acid, or blends of natural and synthetic textile materials, such as blends of cotton with polyester or polyamide fibers.

[0055] Advantageously, when applied to textiles, the copolymers from the present invention provide the textiles with excellent soft hand feel properties and improved hydrophilicity.

[0056] More advantageously, the copolymers according to the invention can be used with all types of textiles, which means that when applied to different textiles, regardless of the type of textile, these copolymers exhibit improved softness and hydrophilic properties.

[0057] It is well known that cellulose-based textiles are inherently hydrophilic, while synthetic textile materials such as polyester textiles are inherently hydrophobic.

[0058] In addition to providing an excellent soft hand feel, the copolymers according to the present invention have the advantage of not reducing the hydrophilicity of the cellulose-based textiles to which they are applied, and also improve the hydrophilicity of synthetic textile materials such as polyester textiles to which they are applied.

[0059] As used herein, the terms "softener," "textile finishing product," and "textile finishing product" have the same meaning and are used interchangeably. According to the invention, the terms "softener," "textile finishing product," and "textile finishing product" refer to copolymers according to the invention obtained by polymerizing organosilicon monomers, polyglycidyl ether monomers (preferably diglycidyl ether monomers), and secondary amino compounds, which, when applied to textiles, impart improved softness and hydrophilicity to the textile.

[0060] As used herein, the terms "soft hand feel" and "softness" refer to the properties of textiles treated with the copolymers according to the invention. The soft hand feel of textiles treated with the copolymers according to the invention is a tactile assessment or hand feel assessment. The soft hand feel of the textiles treated according to the invention is assessed by a hand feel panel, and the tested textiles are ranked from softest to roughest (1 being the softest).

[0061] In an embodiment, the linear random copolymer according to the invention is end-capped with a terminal secondary amine group.

[0062] As used in this invention, the terms "terminated linear random copolymer" or "terminated copolymer" refer to a copolymer chain according to the invention, which has a terminal amine group, particularly a secondary amine group, at each end of its chain. This terminal amine group, particularly the secondary amine group, originates from the reaction between the terminal epoxy group of the copolymer derived from an organosilicon monomer or from a polyglycidyl ether monomer, preferably a diglycidyl ether monomer, and the corresponding amine compound, particularly the secondary amine compound.

[0063] In one embodiment, the copolymer according to the invention is capped with terminal amine groups, preferably secondary amine groups.

[0064] Amine compounds, especially secondary amine compounds, may be the same as or different from the amine compounds used in the polymerization reaction.

[0065] Preferably, according to the invention, the terminal amine group, especially the secondary amine group, originates from the reaction between the terminal epoxy group of the copolymer derived from the organosilicon monomer or from the polyglycidyl ether monomer, preferably the diglycidyl ether monomer, and the amine compound.

[0066] Therefore, in a preferred embodiment, the copolymer according to the invention is end-capped with a compound having the general formula (IIIa), (IIIb) or (IIIc):

[0067] (IIIa)

[0068] in

[0069] R 1 To R 6 Independently selected from -H, -Me, Et, Pr, with R preferred. 1 To R 6 It is -H.

[0070] (IIIb); or

[0071] (IIIc)

[0072] Examples of amine compounds of formula (IIIa) are piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,3-dimethylpiperazine, trans-2,3-dimethylpiperazine, 2,6-dimethylpiperazine, and homopiperazine.

[0073] An example of an amine compound of formula (IIIb) is 1,3-bis(4-piperidinyl)propane.

[0074] Examples of amine compounds of formula (IIIc) are N,N-dimethyl-1,8-octanediamine, N,N'-dimethyl-1,6-hexanediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-dimethylethylenediamine, N,N-diethylethylenediamine, N,N'-diisopropylethylenediamine, N,N-diisopropyl-1,3-propanediamine, 1,5-bis(methylamino)-3-oxapentane, and N,N-bis[3-(methylamino)propyl]methylamine.

[0075] Preferably, the copolymer according to the invention is end-capped with a compound according to formula (IIIa) as defined above, wherein R 1 To R 6 Independently selected from -H, -Me, Et, Pr, with R preferred. 1 To R 6 It is -H.

[0076] Preferably, the copolymer according to the invention is end-capped with piperazine.

[0077] The “end-capping” of the copolymer as described above, using an amine, specifically a secondary amine, such as a secondary amine represented by any of formulas (IIIa), (IIIb), or (IIIc), more preferably a piperazine, has the advantage that the interaction between the copolymer according to the invention and the fiber surface is improved. This interaction is particularly improved when the copolymer according to the invention is used in a (slightly) acidic environment such that the terminal amine groups acquire a positive charge.

[0078] In a preferred embodiment, the end-capping amine group of the copolymer according to the invention is a quaternary ammonium group.

[0079] The copolymers according to the invention further comprise tertiary amine groups. These tertiary amine groups originate from the reaction between an epoxy group derived from an organosilicon monomer or from a polyglycidyl ether monomer, preferably a diglycidyl ether monomer, and an amine compound in the copolymer according to the invention. In contrast to the presence of terminal secondary amine groups at each end of the copolymer, the tertiary amine groups are contained within the linear backbone of the copolymer and link the organosilicon monomer and the polyglycidyl ether monomer, preferably a diglycidyl ether monomer, together.

[0080] In a preferred embodiment, the end-capped amino groups and tertiary amino groups of the copolymer according to the invention are in the form of quaternary ammonium groups.

[0081] In the embodiments, the linear random copolymer according to the invention contains 5 to 95% by weight of organosilicon monomers in the copolymer, preferably 65 to 85%, more preferably 70 to 80%.

[0082] In the embodiments, the linear random copolymer according to the invention has a molar percentage of organosilicon monomers in the copolymer of 0.44 to 24%, preferably 5 to 21%, more preferably 10 to 17%.

[0083] In a preferred embodiment, the linear random copolymer according to the present invention has the following molar percentages:

[0084] The copolymer contains 0.44% to 24% organosilicon monomer, preferably 5% to 21%, more preferably 10% to 17%.

[0085] - The amine compound in the copolymer is 46 to 55%, preferably 48 to 53%, more preferably 49 to 52%, and

[0086] - The copolymer contains 20% to 50% polyglycidyl ether monomer, preferably 25% to 44%, and more preferably 30% to 39%.

[0087] The molar percentage of monomers in a copolymer is a direct result of adjusting the amount of monomers used to synthesize the copolymer.

[0088] Preferably, the amine compound is used in an excess of at least 0.1% molar relative to the organosilicon monomer and the polyglycidyl ether, more preferably at least 5% molar excess, to achieve end-capping with the amine compound.

[0089] Advantageously, the linear random copolymer according to the invention has the following molar percentages:

[0090] The copolymer contains 10% to 17% organosilicon monomers.

[0091] - The amine compound in the copolymer is 49% to 52%, and

[0092] - The copolymer contains 30 to 39% polyglycidyl ether monomer, preferably diglycidyl ether monomer.

[0093] In the embodiments, the linear random copolymer according to the invention contains a polyglycidyl ether monomer in the copolymer at a weight percentage of 5 to 95%, preferably 15 to 60%, more preferably 18 to 34%.

[0094] In a preferred embodiment, the linear random copolymer according to the present invention has the following weight percentages:

[0095] The copolymer contains 5% to 95% organosilicon monomers, preferably 65% ​​to 85%, more preferably 70% to 80%.

[0096] - The amine compound in the copolymer is 1 to 10%, preferably 1.5 to 7%, more preferably 2 to 5%, and

[0097] - The copolymer contains 5% to 95% polyglycidyl ether monomer, preferably 15% to 60%, more preferably 18% to 34%.

[0098] In the embodiments, the mass ratio of organosilicon monomer to polyglycidyl ether monomer, preferably diglycidyl ether monomer, in the copolymer according to the invention is 51 to 97 by weight, preferably 60 to 95, and more preferably 70 to 90.

[0099] The mass ratio of monomers in all aspects of this disclosure can be adjusted to manipulate the properties of the copolymer as desired.

[0100] For example, the mass ratio of monomers can be 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 organosilicon monomers to polyglycidyl ether monomers, preferably diglycidyl ether monomers. Specifically, the mass ratio of monomers can be 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, and 99:1 by weight of organosilicon monomers to polyglycidyl ether monomers, preferably diglycidyl ether monomers.

[0101] In a preferred embodiment, the copolymer according to the invention is derived from the copolymerization of at least the following substances:

[0102] - An organosilicon monomer containing at least two functional epoxy groups,

[0103] - A polyglycidyl ether monomer comprising at least two functional epoxy groups, preferably a diglycidyl ether monomer, and

[0104] - An amine compound containing at least two functional secondary amine groups,

[0105] The mass ratio of organosilicon monomer to polyglycidyl ether monomer, preferably diglycidyl ether monomer, is 51 to 97 by weight.

[0106] In an 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 using polystyrene calibration.

[0107] Contrary to common expectations, these low PDI values ​​are surprisingly obtained without much post-processing, as the polymer is obtained directly from the crude material after solvent removal without precipitation.

[0108] In embodiments, 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.

[0109] The term "number-average molecular weight" as used throughout this specification refers to the number-average molecular weight obtained by size exclusion chromatography, specifically calibrated using polystyrene. For example, a measurement method using size exclusion chromatography with polystyrene calibration is described in the literature (Fontanille, M.; Gnanou, Y., Chimie et physico-chimie des polymeres [Chemistry and physical chemistry of polymers], 2nd edition; Dunod: 2010; p. 546).

[0110] As used in this article, the term "average" refers to the exponential average, unless otherwise stated.

[0111] The advantage of the copolymer according to the invention is that it has an acceptable viscosity, which allows manufacturers to handle it easily without any stickiness issues.

[0112] In the context of this invention, "acceptable viscosity" should be understood as a viscosity of less than 25,000 mPas, particularly 16,000 to 20,000 mPas, which allows the operator to handle the copolymer without any stickiness issues. A copolymer with acceptable viscosity according to the invention also refers to a copolymer that is easily processable, meaning that the copolymer according to the invention is readily soluble in an aqueous diluent or dispersed in an emulsion or dispersion, and then applied to textiles.

[0113] The term "viscosity" refers to Brinell viscosity expressed in mPa·s. Viscosity is measured using a Brinell viscometer at 2000 rpm. Measurements are taken at 25°C and a rotational speed of 300 rpm. The reading is taken after 30 seconds at 25°C.

[0114] Organosilicon monomers

[0115] In the embodiments, the organosilicon monomer according to the present invention is a capped epoxy organosilicon.

[0116] The term "terminated epoxy silicone" as used in this invention refers to a siloxane chain with terminal epoxy groups at each end of its chain.

[0117] In the embodiments, the organosilicon monomer according to the present invention has the general formula (I):

[0118] (I)

[0119] in:

[0120] R is a C1-C8 alkyl group, preferably a linear C1-C8 alkyl group, more preferably a C1-C3 alkyl group, and even more preferably a methyl group;

[0121] X is a C1-C20 alkyl group, preferably a linear C1-C20 alkyl group, more preferably a linear C1-C5 alkyl group, and even more preferably n-propyl.

[0122] Y is a polyalkylene glycol or oxygen.

[0123] Y is preferably linear polyethylene glycol, more preferably monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or pentaethylene glycol, and most preferably tetraethylene glycol.

[0124] "Ci-Cj alkyl" refers to a saturated linear or branched hydrocarbon chain containing i to j carbon atoms.

[0125] m is an integer from 30 to 200, preferably from 40 to 190; more preferably from 45 to 185.

[0126] In a particularly preferred embodiment, the organosilicon according to the invention is based on (Ia):

[0127] (Ia)

[0128] m is an integer from 30 to 300, preferably from 50 to 300; more preferably from 70 to 290.

[0129] n is an integer from 1 to 8, preferably from 1 to 5; more preferably from 2 to 4.

[0130] In the embodiments, the organosilicon monomer according to the present invention has the general formula (Ib):

[0131] (Ib)

[0132] Where m is an integer from 30 to 200, preferably from 40 to 190; more preferably from 45 to 185.

[0133] "C1-C8 alkyl" refers to a saturated linear or branched hydrocarbon chain containing 1 to 8 carbon atoms. Preferably, the hydrocarbon chain is linear. Preferably, the hydrocarbon chain contains 1 to 3 carbon atoms. Preferably, the C1-C8 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. More preferably, the C1-C11 alkyl is selected from the group consisting of methyl, ethyl, and n-propyl. Advantageously, the C1-C8 alkyl is methyl.

[0134] "C1-C20 alkyl" refers to a saturated linear or branched hydrocarbon chain containing 1 to 20 carbon atoms. Preferably, the hydrocarbon chain is linear. Preferably, the hydrocarbon chain contains 1 to 4 carbon atoms. Preferably, the C1-C20 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, and n-butyl. More preferably, the C1-C20 alkyl is n-propyl.

[0135] According to an embodiment, the organosilicon monomer according to the invention is a mixture of at least two different organosilicon monomers of formula (I). Preferably, the organosilicon according to the invention is a mixture of two different organosilicon monomers of formula (I).

[0136] According to another embodiment, the organosilicon monomer according to the invention consists of a single organosilicon monomer of formula (I).

[0137] Polyglycidyl ether monomer

[0138] In the embodiments, the polyglycidyl ether monomer according to the present invention is a diglycidyl ether monomer of general formula (II):

[0139] (II)

[0140] in:

[0141] R 1 The group consisting of free-H, -OH, and C1-C8 alkyl groups is preferred, the group consisting of free-H and linear C1-C8 alkyl groups is more preferred, the group consisting of free-H and C1-C3 alkyl groups is even more preferred, and R is preferably H;

[0142] R 2 The group consisting of free-H, -OH, and C1-C8 alkyl groups is preferred, the group consisting of free-H and linear C1-C8 alkyl groups is more preferred, the group consisting of free-H and C1-C3 alkyl groups is even more preferred, and R is preferably H;

[0143] k is an integer from 1 to 3, more preferably k is 1 or 2;

[0144] n is an integer from 1 to 20, preferably from 2 to 15; more preferably from 6 to 11;

[0145] Preferably, R 1 Selected from -H or -Me;

[0146] R 2 Selected from -H, -Me, or,

[0147] k is 1 or 2;

[0148] n is between 6 and 11.

[0149] According to a preferred embodiment, the diglycidyl ether monomer of formula (II) according to the present invention is selected from the diglycidyl ether monomers of formula (IIa) or (IIb):

[0150] (IIa) or

[0151] (IIb);

[0152] in:

[0153] R 1 The group consisting of free-H and C1-C8 alkyl groups is preferred, the group consisting of free-H and linear C1-C8 alkyl groups is even more preferred, and the group consisting of free-H and C1-C3 alkyl groups is even more preferred.

[0154] n is an integer from 1 to 20, preferably from 2 to 15; more preferably from 6 to 11;

[0155] o is an integer from 1 to 20, preferably 2 to 15; more preferably 6 to 11; and

[0156] Diglycidyl ether monomers of formula (II), (IIa), or (IIb) are well known to those skilled in the art and are commercially available. Particularly suitable diglycidyl ether monomers include, for example, those from Huntsman (Araldite). ® DY 3601 or Araldite ® DY 3602).

[0157] According to the embodiments, the polyglycidyl ether monomer according to the invention is a mixture of at least two different diglycidyl ether monomers of formula (II), particularly a mixture of two different diglycidyl ether monomers of formula (IIa) or (IIb).

[0158] Preferably, the polyglycidyl ether monomer according to the invention is a mixture of two different diglycidyl ether monomers of formula (II).

[0159] Advantageously, the polyglycidyl ether monomer according to the invention is a mixture of two different diglycidyl ether monomers of formula (IIa) or (IIb).

[0160] According to another embodiment, the polyglycidyl ether monomer according to the invention consists of a single diglycidyl ether monomer of formula (II).

[0161] Preferably, the polyglycidyl ether monomer according to the present invention consists of a single diglycidyl ether monomer of formula (IIa) or (IIb).

[0162] Specifically, the polyglycidyl ether monomer according to the present invention comprises or consists of compounds of the following formula:

[0163] (IIa) or

[0164] Where R 1 It is methyl and n is an integer from 1 to 20, preferably from 2 to 15; more preferably from 6 to 11.

[0165] This polyoxypropylene diglycidyl ether, as a comonomer, produces copolymers according to the invention with optimal performance.

[0166] Specifically, polyoxypropylene diglycidyl ether as a comonomer has advantages over polyoxyethylene diglycidyl ether as a comonomer, namely, the resulting copolymer is easier to emulsify. The disadvantage of copolymers containing polyoxyethylene diglycidyl ether as a comonomer is that they exhibit low overall performance and are difficult to emulsify because they form a gel upon contact with water due to strong hydrogen bonds.

[0167] amine compounds

[0168] In embodiments, the amine compound according to the invention comprises at least two functional secondary amine groups. Preferably, the amine compound according to the invention comprises two functional secondary amine groups. The secondary amine groups of the amine compound according to the invention react with epoxy groups from a polyglycidyl ether monomer (preferably a diglycidyl ether monomer) or from an organosilicon monomer to form a linear random copolymer according to the invention. Using an amine compound comprising functional secondary amine groups as a linker between monomers advantageously allows control over the copolymer structure during polymerization, and thus allows obtaining a linear copolymer according to the invention.

[0169] In a preferred embodiment, the amine compound according to the invention is a cyclic or linear amine compound. Advantageously, the amine compound according to the invention is a cyclic amine compound.

[0170] In a preferred embodiment, the two functional secondary amine groups of the amine compound according to the invention are part of the skeleton of the amine compound.

[0171] Advantageously, the two functional secondary amine groups of the amine compound according to the invention are part of the cyclic skeleton of the amine compound.

[0172] In a preferred embodiment, the amine compound according to the invention is substituted with at least one substituent selected from the group consisting of C1-C8 alkyl, halogen or -OH.

[0173] As used in this article, the term "halogen" refers to a fluorine atom, a chlorine atom, or a bromine atom.

[0174] In embodiments, the amine compounds according to the invention have the general formula (IIIa), (IIIb) or (IIIc):

[0175] (IIIa)

[0176] in

[0177] R 1 To R 6Independently selected from -H, -Me, Et, Pr, with R preferred. 1 To R 6 It is -H.

[0178] (IIIb); or

[0179] (IIIc)

[0180] Examples of amine compounds of formula (IIIa) are piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,3-dimethylpiperazine, trans-2,3-dimethylpiperazine, 2,6-dimethylpiperazine, and homopiperazine.

[0181] An example of an amine compound of formula (IIIb) is 1,3-bis(4-piperidinyl)propane.

[0182] Examples of amine compounds of formula (IIIc) are N,N-dimethyl-1,8-octanediamine, N,N'-dimethyl-1,6-hexanediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-dimethylethylenediamine, N,N-diethylethylenediamine, N,N'-diisopropylethylenediamine, N,N-diisopropyl-1,3-propanediamine, 1,5-bis(methylamino)-3-oxapentane, and N,N-bis[3-(methylamino)propyl]methylamine.

[0183] According to the embodiments, the amine compound according to the invention is a mixture of at least two different amine compounds of formula (IIIa), (IIIb) or (IIIc).

[0184] Preferably, the amine compound according to the invention is a mixture of two different amine compounds of formula (IIIa), (IIIb) or (IIIc).

[0185] According to another embodiment, the amine compound according to the invention consists of a single amine compound monomer of formula (IIIa), (IIIb) or (IIIc).

[0186] The aforementioned amine compounds can be used to construct copolymers and form polymer end caps.

[0187] Method for preparing copolymers according to the present invention

[0188] The present invention also relates to a method for preparing copolymers according to the invention, comprising at least one polymerization step a), wherein at least the following substances are contacted in a solvent:

[0189] - Organosilicon monomers containing at least two functional epoxy groups,

[0190] - Polyglycidyl ether monomer, preferably diglycidyl ether monomer, and

[0191] - An amine compound containing at least two functional secondary amine groups.

[0192] Preferably, in the first step, an organosilicon monomer containing at least two functional epoxy groups is reacted with an amine compound containing at least two 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.

[0193] According to a preferred embodiment, the solvent used in step a) has a boiling point of less than 100°C, preferably less than 90°C, and more preferably 70°C to 88°C.

[0194] 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).

[0195] According to another preferred embodiment, the polymerization step a) is carried out in an inert atmosphere such as nitrogen.

[0196] In one embodiment, the method further includes 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 for the acquisition of a copolymer ready for use without further purification.

[0197] Preferably, distillation step b) is carried out at atmospheric pressure.

[0198] As used in this article, the term "atmospheric pressure" means approximately 1 atm.

[0199] In a preferred embodiment, distillation step b) is carried out at the boiling point temperature of the solvent.

[0200] Advantageously, the temperature of distillation step b) is less than 100°C, preferably less than 90°C, and more preferably 70°C to 88°C. Preferably, the pressure is gradually reduced to 500 mbar to completely remove the solvent.

[0201] In one embodiment, the method further includes a quaternization step (c) of the copolymer obtained according to the invention in step b).

[0202] Preferably, the quaternization step c) is a procedure that introduces an additional methyl group onto the N atom after copolymer synthesis. This procedure provides an additional positive charge at the methylated N atom.

[0203] The hydrophilicity and surface interaction properties of the copolymer are improved through the quaternization step.

[0204] In one embodiment, the method further includes adding a surfactant prior to distillation step b) to avoid high viscosity and improve the handling and processing of the copolymer and its storage properties.

[0205] Composition and uses

[0206] The copolymers according to the present invention are intended for use as textile softeners.

[0207] The present invention also relates to compositions comprising at least one copolymer according to the invention. The composition is applied to textiles to provide the textiles with improved softness and hydrophilic properties.

[0208] In the embodiments, the composition is in the form of an emulsion, an aqueous diluent, or a suspension, preferably in the form of an aqueous emulsion.

[0209] In a preferred embodiment, the copolymer is present in the composition according to the invention at 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 are included within the scope of this invention.

[0210] In an embodiment, the composition according to the invention comprises at least one surfactant.

[0211] The term "surfactant" refers to a substance that reduces the surface tension of a liquid. Typical examples useful for application to textiles are anionic or nonionic surfactants, such as fatty alcohol ethoxylates and fatty alcohol alkoxylates, which act as wetting and rewetting agents. The nonionic surfactants mentioned in this invention are linear or branched alkoxylated alcohols having a C8-C18 carbon chain and an ethoxylation / propoxylation degree of 1-12. Anionic surfactants are selected from sulfates, sulfonates, and phosphates of linear or branched alkyl chains with or without alkoxy groups.

[0212] Advantageously, the composition according to the invention comprises at least:

[0213] - At least one copolymer according to the invention, having a concentration of 0.1% to 99.9% by weight, preferably 1% to 99% by weight, more 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; and

[0214] - At least one surfactant, the concentration of which is 0.1 to 10% by weight based on the total weight of the composition, preferably 0.5% to 10% by weight, more preferably 1% to 9% by weight, more preferably 2.5% to 6% by weight, and most preferably 3% to 5% by weight.

[0215] Unless otherwise stated, the “weight percentage” (expressed as % by weight or weight %) of copolymers or surfactants in a composition refers to the weight of the compounds used based on the total weight of the composition.

[0216] In another embodiment, the composition according to the invention may further comprise a mixture of a nonionic surfactant and / or anionic surfactant, wherein the nonionic surfactant is an alkoxylated alcohol containing a C8-C18 linear or branched carbon chain, and the alkoxy group is ethoxy and / or propoxy, with 1 to 11 repeating units. The anionic surfactant is preferably selected from the group consisting of carboxylates, sulfates, sulfonates, or phosphates of C8 to C18 linear or branched alkyl chains, with or without alkoxy groups.

[0217] In a preferred embodiment, the composition according to the invention may further comprise an organic solvent or solubilizer, preferably having hydroxyl functionality and selected from the group consisting of C2 to C10 monohydroxy alcohols or polyhydroxy alcohols having 1-3 hydroxyl groups and 0-4 ether bonds, such as butyl diethylene glycol, polyethylene glycol / propylene glycol, diethylene glycol or sodium dodecylbenzenesulfonate.

[0218] Preferably, the composition according to the invention comprises butyl diethylene glycol.

[0219] The present invention also relates to a method of treating textiles with the compositions of the present invention or copolymers of formula (I) according to the present invention, wherein the compositions or copolymers according to the present invention are applied to or incorporated into the textiles.

[0220] The present invention also relates to the use of compositions or copolymers according to the invention in treating textiles to simultaneously improve the softness and hydrophilicity of the textiles.

[0221] The present invention also relates to textiles treated with compositions or copolymers according to the present invention.

[0222] Example

[0223] The following commercial products were used in the given embodiments:

[0224] -Commercial Product 1: Microemulsion of amino-functionalized polydimethylsiloxane

[0225] -Commercial Product 2: Macroemulsion of amino-functionalized polydimethylsiloxane

[0226] -Commercial Product 3: Microemulsion of amino-organic silicone block copolymer

[0227] -Commercial Product 4: Microemulsions of cationic polysiloxane compounds,

[0228] -Commercial Product 5: Microemulsions of hydrophilic polysiloxane compounds,

[0229] -Commercial Product 6: Microemulsions of hydrophobic polysiloxane compounds,

[0230] -Knittex FEL (a reactive crosslinking agent based on modified dimethyloldihydroxyethylene urea)

[0231] -Knittex CAT.MO (crosslinking catalyst)

[0232] -Marlipal 13 / 70: Ethoxylated isotridecyl alcohol (a nonionic surfactant based on ethoxylated C13 alcohol)

[0233] -Lutensol TO-6: (Nonionic surfactant, based on saturated isoc13 alcohol)

[0234] Preparation of copolymers according to the present invention

[0235] In a 500 ml three-necked flask equipped with a mechanical stirrer, feeding funnel, thermometer, and reflux cooler, piperazine (2.1 mol) was added and mixed with isopropanol under a nitrogen atmosphere until all solids dissolved. An organosilicon monomer (0.59 mol) was stirred in and the reaction mixture was refluxed for 1.5 hours. The reaction mixture was then cooled to <40°C and an epoxy-functionalized diol monomer (1.41 mol) was added with stirring. The resulting mixture was heated to reflux and continuously stirred under a nitrogen atmosphere for another 2 hours. The resulting mixture was then cooled to room temperature and the isopropanol was removed by distillation (from 900-200 mbar over 100 minutes) to obtain the copolymer according to the invention in 99.9% yield. The obtained copolymer was used as is in the emulsion described below without any further purification.

[0236] Table 1. Amounts of copolymers 1 to 3 according to the present invention

[0237]

[0238] 1 diglycidyl ether monomer of polyoxypropylene glycol

[0239] 2 Epoxy-terminated polydimethylsiloxane with a molecular weight of 4000 g / mol

[0240] 3Epoxy-terminated polydimethylsiloxane with a molecular weight of 6000 g / mol

[0241] 4 Epoxy-terminated polydimethylsiloxane with a molecular weight of 8000 g / mol

[0242] Preparation of emulsions comprising the copolymers according to the present invention and comparative copolymers

[0243] The emulsion is prepared using the following steps:

[0244] 1. Combine Marlipal (3 g) 13 / 70 and polymer (10-15 g) and homogenize them well at room temperature (mix for 10 minutes).

[0245] 2. Add butyl diethylene glycol (2 g) to the above mixture and homogenize it well at room temperature (mix for 10 minutes).

[0246] 3. Add approximately 80 g of water in 7-8 portions over 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 g glycolic acid (57%), and add 0.08 g of the preservative "ACTICIDE" at a temperature below 35°C. ® SPX.

[0247] Evaluation of the wicking properties of cotton textiles treated with the emulsion according to the present invention and comparative emulsions.

[0248] The results are given in Tables 2 through 7.

[0249] Table 2. Evaluation of wicking and hydrophilicity of 100% cotton textile materials (cotton shirts) treated with the emulsion according to the present invention and comparative emulsions.

[0250]

[0251] Table 3. Evaluation of wicking and hydrophilicity of 100% cotton textile materials (cotton shirts and easy-care products) treated with the emulsion according to the present invention and comparative emulsions.

[0252]

[0253] Table 4. Evaluation of wicking and hydrophilicity of 100% cotton textile materials treated with the emulsion according to the present invention and comparative emulsions.

[0254]

[0255] Table 5. Evaluation of wicking and hydrophilicity of 100% cotton textile materials treated with the emulsion according to the present invention and comparative emulsions.

[0256]

[0257] Table 6: Evaluation of wicking and hydrophilicity of 100% cotton textile materials treated with the emulsion according to the present invention and comparative emulsions.

[0258]

[0259]

[0260] Evaluation of the wicking properties of polyester textiles treated with the emulsion according to the present invention and comparative emulsions.

[0261] The wicking and hydrophilicity of materials treated with the emulsion according to the invention and comparative emulsions before and after washing (5 times at 40°C) are given in Tables 7 and 8.

[0262] Table 7. Evaluation of wicking and hydrophilicity of 100% polyester textile materials treated with the emulsion according to the present invention and comparative emulsions.

[0263]

[0264] Table 8. Evaluation of wicking and hydrophilicity of 100% polyester textile materials treated with the emulsion according to the present invention and comparative emulsions.

[0265]

[0266]

[0267] Evaluation of the hand feel (softness) of cotton and polyester textiles treated with the emulsion according to the present invention and by comparison.

[0268] The softness and hydrophilicity of cotton and polyester materials treated with the emulsion according to the invention and comparative emulsions before and after washing (5 times at 40°C) are given in Table 9.

[0269] Table 9: Evaluation of the hand feel and hydrophilicity of cotton and polyester textile materials treated with the emulsion according to the present invention and comparative emulsions

[0270]

[0271] Example 2:

[0272] Preparation of copolymers according to the present invention

[0273] In a 500 ml three-necked flask equipped with a mechanical stirrer, feeding funnel, thermometer, and reflux cooler, 1.5 g piperazine and 7.5 g dodecanoic acid were stirred in 25 ml butylcarbitol until the mixture was homogenized. Then, 125 g of polyether silicone monomer (in two parts) was added to the mixture. The resulting mixture was heated at 80 °C under a nitrogen atmosphere and stirred continuously for 6 hours. The resulting mixture was then cooled at room temperature to obtain the copolymer according to the invention in 100% yield. The obtained copolymer was used as is in the emulsions described in Tables 10 and 11 below without any further purification.

[0274] Preparation of emulsions comprising the copolymers according to the present invention and comparative copolymers

[0275] The emulsion is prepared using the following steps:

[0276] 1. Add Lutensol TO 6 (9-12 g) to water acidified with 0.3-0.5 g of 60% acetic acid and homogenize it well at room temperature (mix for 10 minutes).

[0277] 2. Add 3 g of butyl diethylene glycol to the above mixture and homogenize it well at room temperature (mix for 10 minutes).

[0278] 3. If it is necessary to increase the hydrophilicity of the formulation, add 12-17 g of glycerol to the above mixture and homogenize it well (10 minutes at room temperature).

[0279] 4. Add the silicone polymer (15-29 g) and heat at 65°C for 1 hour, homogenizing the mixture to obtain the final emulsion. Cool and adjust the water to 100 g.

[0280] Table 10: Amounts of components in emulsions

[0281]

[0282] Table 11: Components of the Formulation

[0283]

[0284] Working Example:

[0285] The prepared sample was applied to 100% cotton fabric by padding, using a liquid-hold ratio of 13-15%, and the treated fabric was dried at 130°C for 3 minutes.

[0286] Table 12: Absorbency and wicking height of cotton plain knit fabrics produced by wet-to-wet continuous weave

[0287]

[0288] Table 13: Absorbency and wicking height of polyester:cotton (60:40) blends produced by wet-to-wet continuous process

[0289]

[0290] Table 14: Initial and 3HL Feel Scores

[0291]

[0292] Table 15: Results of color fastness to rubbing after initial and 3HL tests

[0293]

[0294] Feel evaluation:

[0295] Samples were taken from dyed, unfinished terry towels, cotton knitwear, and polyester / cotton (60:40) single-sided plain knit fabrics. These samples were impregnated with an emulsion containing 40 g / L of formulations 1 to 12, followed by acetic acid-acidified aqueous solution. The emulsions were then applied to a laboratory pad dyeing machine to achieve a specific wet-liquid ratio by weight, and subsequently dried at 120–130°C for 3–7 minutes. The hand feel properties of the emulsion-treated test fabrics were evaluated. For meaningful results, evaluation was conducted by at least five reviewers. The results shown above are on a softness scale of 1 to 5, with 5 being the least soft and 1 being the softest.

[0296] hydrophilic :

[0297] The hydrophilicity shown in Tables 7 and 8 was then evaluated through a water drop test, and the water retention on the terry towel was measured by calculating the percentage of water absorbed by the towel by pouring 50 ml of water onto it and measuring the amount of water discharged.

[0298] Cusp suction height (AATCC test method 197):

[0299] Cut the fabric into 25 × 15 cm pieces (warp and weft directions) using the sample. Place a ruler vertically against the back of a rectangular dish (see figure) inside the box, with the ruler touching the bottom. Fill the rectangular 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 dish. Secure the ruler to the outside of the dish with tape so that the top of the water surface is at the "0" mm mark on the ruler. Secure the sample to the top of the box with double-sided tape so that the bottom edge just touches the top of the water surface (the same as the "0" mm mark on the ruler), and immediately start a stopwatch or timer. Some lightweight woven, knitted, or hydrophobic fabrics may float on the water surface; in this case, attach a small paper clip or clamp to the end of the sample to be submerged. If paper clips or clamps are used, this should be noted in the report. Monitor the water rise. At 10.0 ± 0.1 min, use a ruler to measure the distance the water has wicked away. Record the distance in centimeters. Alternative wicking times may be used, depending on the intended end use of the fabric. When comparing results, the same wicking time baseline should be used. Repeat the test for two samples from each fabric to minimize error. Take the average of the two readings in the warp and weft directions for reporting.

[0300] Dot test:

[0301] The spots on the treated terry towels were tested using a chlorine dilution at ppm levels. Discoloration was rated on a scale of 1-5, where 5 indicates no discoloration and 1 indicates more discoloration.

[0302] Color fastness to rubbing (AATCC test method 165):

[0303] Device used: Friction meter

[0304] There are two testing methods: wet friction method and dry friction method.

[0305] Dry friction method

[0306] Cut the sample to be tested and the white woven fabric into 2×2 cm pieces. Under controlled conditions, rub the colored test sample held on the base of the rubbing instrument with a white test cloth. Perform 10 rubs on each sample. Evaluate the color transferred to the white test cloth by comparing it with the AATCC 9-level color shift scale or the dyeing gray scale, and assign a grade.

[0307] wet friction method

[0308] Cut the sample to be tested and the white woven fabric into 2×2 cm pieces. Wet the white cloth with distilled water using a dropper. Under controlled conditions, rub the colored test sample held on the base of the rubbery apparatus with the white test cloth. Perform 10 rubs on each sample. Evaluate the color transferred to the white test cloth by comparing it with the AATCC 9-level color shift scale or the dyeing gray scale, and assign a grade.

[0309] result:

[0310] Formulations 8, 9, and 12 exhibited better hand feel and good absorbency on plain knit fabrics. For polyester:cotton blends (60:40), most formulations had a better initial hand feel than Rucofin GES M, and this was also true after 3HL. The wicking height in all formulations was superior to the benchmark, and therefore the performance of the present invention is superior to Rucofin GES M. These compositions are suitable for knitted fabric finishing applications. Formulation 3 will be suitable for applications where hydrophilicity is not required.

[0311] test:

[0312] - Hand feel characteristics (initial and 5 cycles at 40°C) are performed manually (washing is completed according to ISO 6330 washing program 4G); hand feel is evaluated by testers in a group test. Lower values ​​are better. For example, if there are 5 samples, 1 is the best and 5 is the worst score. The values ​​are added together to give the total value.

[0313] - Color fastness to rubbing, according to DIN EN or ISO 105-X12.

[0314] - Cumulus test (initial and 5 times at 40°C), according to DIN 53924.

[0315] -TEGEWA drop test (initial and 5 times at 40°C), TEGEWA drop test method:

[0316] 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 droplet to disappear is measured and recorded as the wetting time. Samples dried before sampling should be air-dried first. All samples should reach moisture equilibrium in standard atmosphere at 21±1℃ and 65±2% relative humidity.

[0317] The fabric is installed in the ring guide so that the surface is smooth without distorting the material's structure.

[0318] A funnel with a pipette is placed over a ring on which textiles are fixed, and a drop (droplet size 0.05 ml ± 10%, drop height: 40 mm) of distilled water (with or without dye) is dropped onto the test sample at 21 ± 3 °C. The time required for the fabric surface to lose the specular reflection caused by the droplet is measured. The water droplet is determined by positioning the ring between the observer and the light source (such as a window or laboratory spotlight) at an angle where the specular reflection of light from the flat droplet surface can be clearly seen. As the droplet is gradually absorbed, the area of ​​the tiny specular reflection decreases and eventually disappears completely, leaving only a dark wet spot. At this point, the watch is stopped and the elapsed time is recorded. The test is stopped when the wetting time exceeds 1 minute. Five readings are taken and the average is calculated.

[0319] - Yellowing with temperature (Fixotest), whiteness measured after thermal contact (internal method).

[0320] - Whiteness, measured according to GANZ.

[0321] - Injection stability; internal testing.

Claims

1. Linear random copolymers, derived from at least one copolymer: - Organosilicon monomers containing at least two functional epoxy groups, - Polyglycidyl ether monomer, preferably diglycidyl ether monomer, and - An amine compound containing at least two functional secondary amine groups.

2. The copolymer according to claim 1, wherein it is capped with terminal amine groups, preferably secondary amine groups.

3. The copolymer according to any one of the preceding claims, wherein the weight percentage of the organosilicon monomer in the copolymer is 5 to 95%, preferably 65 to 85%, more preferably 70 to 80%.

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

5. The copolymer according to any one of the preceding claims, wherein the organosilicon monomer has the general formula (I): (I) in: R is a C1-C8 alkyl group, preferably a linear 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 linear C1-C20 alkyl group, more preferably a linear C1-C4 alkyl group, and even more preferably n-propyl. Y is a polyalkylene glycol or oxygen; Y is preferably linear polyethylene glycol, more preferably monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or pentaethylene glycol, most preferably tetraethylene glycol, and m is an integer from 30 to 200, preferably from 40 to 190; more preferably from 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): (II) in: R 1 The group consisting of free-H and C1-C8 alkyl groups is preferred, the group consisting of free-H and linear C1-C8 alkyl groups is even more preferred, and the group consisting of free-H, -OH and C1-C3 alkyl groups is even more preferred. R 2 The group consisting of free-H and C1-C8 alkyl groups is preferred, the group consisting of free-H and linear C1-C8 alkyl groups is even more preferred, and the group consisting of free-H and C1-C3 alkyl groups is even more preferred. k is an integer from 1 to 3, more preferably k is 1 or 2. n is an integer from 1 to 20, preferably from 2 to 15; more preferably from 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): (IIIa); (IIIb); or (IIIc) in: R 1 To R 6 Independently selected from -H, -Me, Et, Pr, with R preferred. 1 To R 6 Yes, it's -H.

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: - Organosilicon monomers containing at least two functional epoxy groups, - Polyglycidyl ether monomer, preferably diglycidyl ether monomer, and - An amine compound containing at least two functional secondary amine groups.

10. The method according to claim 9, wherein the solvent used in step a) has a boiling point of less than 100°C, preferably less than 90°C, more preferably 70°C to 88°C.

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

12. The method according to any one of the preceding claims, wherein the temperature of the distillation step b) is less than 100°C, preferably less than 90°C, and more preferably 70°C to 88°C.

13. The method according to any one of the preceding claims further includes 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 procedure of introducing an additional methyl group onto the N atom after copolymer synthesis, the procedure providing an additional positive charge at the methylated N atom.

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 diluent or a suspension, preferably in the form of an emulsion.

16. The composition according to claim 15, wherein the copolymer is present in the composition at a concentration of 0.1% to 99.9% 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.

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

18. The 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 in treating textiles to simultaneously improve the softness and hydrophilicity of said textiles.

19. Textiles treated with the composition according to any one of claims 15 to 17 or the copolymer according to any one of claims 1 to 8.

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