CN111479855A - Copolymers of polyalkyleneimines and polysiloxanes and compositions containing the same - Google Patents
Copolymers of polyalkyleneimines and polysiloxanes and compositions containing the same Download PDFInfo
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- CN111479855A CN111479855A CN201880079944.9A CN201880079944A CN111479855A CN 111479855 A CN111479855 A CN 111479855A CN 201880079944 A CN201880079944 A CN 201880079944A CN 111479855 A CN111479855 A CN 111479855A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/65—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups
- D06M15/652—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups comprising amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
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- Textile Engineering (AREA)
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- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention provides copolymers of polyalkyleneimines and polysiloxanes, textile softening compositions comprising said copolymers, methods of treating textiles with said copolymers, the use of said copolymers for treating textiles and textile softening kits comprising said copolymers. Textiles treated with the copolymers were found to have a special hand and improved water resistance.
Description
Technical Field
The present invention relates to a copolymer of polyalkyleneimine and polysiloxane for use as a textile (textile) treatment agent in the textile industry, and in particular to a copolymer of polyalkyleneimine and polysiloxane suitable for use in a textile softening composition or a water repellent composition. Furthermore, the present invention relates to a textile softening composition or a waterproof composition containing the same. The invention also relates to a process comprising the use of such copolymers as textile softeners or water repellents in the textile industry, especially during textile finishing processes.
Prior Art
The hand of the fabric (textile) is the "feel" of the fabric, meaning the feel that is imparted when the fabric is touched. The hand feeling of the textile is texture, drapability, flexibility, wrinkle resistance and the like. "Soft hand" is smooth to the touch and is envisioned as a comfortable wearing fabric and a smooth or fine to the touch fabric is essentially a soft fabric. This may also be referred to as "fine hand".
Textile softeners are treatment agents in the textile industry that make textiles soft, bulky and antistatic, thereby providing them with a soft hand. Silicone oils (silicone oils) are a widely used type of textile softener in the art that can provide a soft and fluffy hand. However, silicone oil textile softeners are typically hydrophobic, which reduces the hydrophilicity of the treated textile and, in turn, reduces the fluffy (buffy) feel of the treated textile.
In recent years, various modified silicone oils, such as amino silicone oils, hydrophilic silicone oils, and the like, have been developed to improve hydrophilicity. These modified silicone oils are widely used in textiles to provide hydrophilic benefits to the treated textiles while maintaining a soft and fluffy hand and antistatic properties.
CN 1919896 a describes a method for preparing amino-modified hydrophilic silicone oil, which comprises reacting low hydrogen silicone oil with polyether in the presence of chain transfer agent and catalyst, and further reacting with amino coupling agent. In this process, an ether mixture of a polyether named F-6 (allyl polyoxyalkylene ether) and allyl glycidyl ether is used as polyether and the amino coupling agent is selected from small molecules such as gamma-aminopropyltriethoxysilane, N- (P-aminoethyl) -gamma-aminopropylmethyldiethoxysilane.
CN104558618A discloses a block-modified silicone represented by the following formula
Wherein n is in the range of 200 to 1000, x + y is in the range of 2 to 50, and m is in the range of 1 to 200.
CN101497697B describes a process for the preparation of water-soluble block silicone oils comprising (1) amidating an amino coupling agent, (2) preparing a silicone intermediate containing terminal hydrogens by reacting octamethylcyclotetrasiloxane and/or low viscosity hydroxy silicone oil with 1,1,3, 3-tetramethyldisiloxane in the presence of the amidated amino coupling agent, (3) preparing a linear block copolymer of polysiloxane-polyether by reacting the product from step (2) with allyl polyether, and (4) aminolyzing the block copolymer from step (3). The amino coupling agent is selected from small molecules such as gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylethyldimethoxysilane.
CN102964601A describes a hydrophilic block silicone oil and a method for its preparation, which method comprises (1) charging 35 to 45 parts of aliphatic polyether diamine, 300 to 340 parts of isopropanol, 360 to 400 parts of epoxy-terminated silicone oil into a reactor, heating to 80 ℃ and holding at that temperature for 8 hours, (2) charging 4 to 6 parts of 20% sulfuric acid and equilibrating for 30 minutes, (3) charging 400 to 450 parts of dipropylene glycol, equilibrating for 30 minutes, and then reducing the pressure to a certain vacuum degree, raising the temperature to 100 ℃, further evacuating (vacumize) to a maximum extent, equilibrating for 30 minutes, reducing the temperature to 50 ℃; (4) 150 to 170 parts of the isomeric alcohol polyoxyethylene ether and 1 to 3 parts of acetic acid are charged and the temperature is lowered to 35 ℃.
Although these silicone oil softeners used as textile finishing agents exhibit excellent flexibility and good durability, there is a drawback of lack of hydrophilicity after finishing processing (although softness has been significantly improved), and hydrophilic silicone oil softeners developed therefor have less soft hand and inferior washing durability.
However, these silicone oil type softeners typically physically adhere to the surface of the treated textile. Thus, over time, by, for example, using the treated textile, washing the treated textile, exposing the treated textile to radiation or light, and the like, the softeners on the textile surface will gradually be removed and their effect will be destroyed. In addition, the soft and bulky hand provided by those silicone oil type softeners is sometimes unsatisfactory.
Accordingly, there remains a need in the marketplace to provide a textile softener and, accordingly, a textile softening composition for use in textile treatment in the textile industry that will provide a particular hand to the treated textile, such as a soft and fluffy hand, and also improve the durability of the soft hand.
Water repellents (e.g., fluorine-containing water repellents) are commonly used as textile treatments to provide water repellent properties to textiles. EP 2205688a1 discloses a method of treating a substrate with a fluorinated water-soluble (meth) acrylate copolymer which imparts water repellency. However, fluorinated compounds used for these applications are harmful to the environment and to the human body. In particular, perfluorinated compounds may reduce the immune and reproductive capacity and are found to be substances causing e.g. thyroid disease disorders (thyroid disease Bar), which were designated as international environmental hazards in Stockholm Party Conference in 2009.
Thus, in order to avoid the above mentioned regulations, there is still a need in the market to provide a waterproofing agent and accordingly a waterproofing composition which is not only harmless to humans and the environment, but also exhibits satisfactory waterproofness.
Disclosure of Invention
It has been found that the above object can be achieved with the copolymers according to the invention, i.e. copolymers of polyalkyleneimines, in particular polyethyleneimines or polypropyleneimines, and epoxy-terminated polysiloxanes, in particular in combination with fixing agents (fixing agents).
The present invention therefore relates to several aspects of copolymers of polyalkyleneimines, in particular polyethyleneimines or polypropyleneimines, and polysiloxanes, in particular their use in the textile industry for textile softening or water repellency.
In a first aspect, the present invention relates to a copolymer of a polyalkyleneimine (in particular a polyethyleneimine or a polypropyleneimine) and an epoxy-terminated polysiloxane, which is used as a textile softener or water repellent, in particular in the textile industry.
In a second aspect, the present invention relates to a textile softening composition comprising as a textile softening agent a copolymer of a polyalkyleneimine, especially a polyethyleneimine or polypropyleneimine, and an epoxy-terminated polysiloxane.
In a third aspect, the present invention relates to a method, in particular an industrial method, for treating a textile, comprising the steps of: the textile softening composition comprising a copolymer of a polyalkyleneimine, especially a polyethyleneimine or a polypropyleneimine, and an epoxy-terminated polysiloxane is contacted with the textile, preferably during the textile finishing process in the textile industry.
In particular, the present invention relates to an industrial process for treating a textile, comprising: a first step of contacting it with a textile softening composition comprising a copolymer of a polyalkyleneimine (especially a polyethyleneimine or polypropyleneimine) and an epoxy-terminated polysiloxane; and contacting the textile with a fixing agent in a second step.
The fixative is preferably selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehydes.
In a fourth aspect, the present invention relates to the use of copolymers of polyalkyleneimines, in particular polyethyleneimines or polypropyleneimines, and epoxy-terminated polysiloxanes for treating textiles during textile finishing processing steps in the textile industry, in particular in the textile industry. In particular, the invention relates to the use of copolymers of polyalkyleneimines, in particular polyethyleneimines or polypropyleneimines, and epoxy-terminated polysiloxanes in combination with fixing agents.
This fixative is preferably selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehydes used for treating textiles in the textile industry.
In a fifth aspect, the present invention relates to a textile softening kit comprising
(A) A copolymer as described above for the first aspect of the invention as a textile softening agent, or a textile softening composition as described above for the second aspect of the invention; and
(B) a fixative agent selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehyde, wherein in the textile softening kit the textile softener and the fixative agent are packaged separately from each other.
In a sixth aspect, the present invention relates to a waterproofing composition containing a copolymer of polyalkyleneimine (especially polyethyleneimine or polypropyleneimine) and epoxy-terminated polysiloxane as a waterproofing agent.
In a seventh aspect, the present invention relates to a method, in particular an industrial method, for treating a textile, comprising the steps of: a waterproofing composition comprising a copolymer of a polyalkyleneimine, especially a polyethyleneimine or a polypropyleneimine, and an epoxy-terminated polysiloxane is contacted with a textile, preferably during textile finishing processes in the textile industry.
In particular, the present invention relates to an industrial process for treating a textile, comprising: a first step of bringing it into contact with a waterproofing composition comprising a copolymer of a polyalkyleneimine (in particular polyethyleneimine or polypropyleneimine) and an epoxy-terminated polysiloxane; and in a second step contacting the textile with a fixing agent.
The fixative is preferably selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehydes.
Without wishing to be bound by any theory, it has been found that with the subject matter of the present invention, the treated textile will have a special hand, e.g., a soft and fluffy hand, and have improved water repellency, while the durability of these desirable characteristics is improved.
It is believed that the synthetic copolymers of polyalkyleneimines, especially polyethyleneimines or polypropyleneimines, and epoxy-terminated polysiloxanes of the present invention, especially with certain additives, such as Epichlorohydrin (ECH), trichlorotriazine and certain dialdehydes, are more strongly fixed to fabrics, especially cotton, by their residual amine groups to contribute to a permanently soft and fluffy hand and improved water repellency.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The expressions "article (a/an)", "the" when used to define terms include both the plural and the singular of the term.
The first aspect of the present invention relates to a copolymer comprising the following structural units per molecule:
(i) at least one polyalkyleneimine structural unit containing an average of at least 10 polymerized C2-C10Alkylene imine units (polymerized C)2-C10Alkyleneimine units), and
(ii) at least one polysiloxane structural unit derived from an epoxy-terminated polysiloxane, which is used as a textile softener or water repellent in the textile industry.
In the following, when referring to a copolymer comprising polyalkyleneimine building blocks and epoxy-terminated polysiloxane building blocks according to this aspect of the invention, the expression "copolymer of the invention" or "copolymer according to the invention" is used.
In one embodiment of the present invention, the polyalkyleneimine structural unit (i) is preferably a polyethyleneimine or polypropyleneimine structural unit.
In the context of the present invention, the term "polyalkyleneimine (polyalkyleneimine)", such as polyethyleneimine and polypropyleneimine, refers to the polyalkyleneimine polymer from which the polyalkyleneimine structural units of the copolymers of the present invention are derived.
In the context of the present invention, the term "polyethyleneimine" refers not only to polyethyleneimine homopolymers, but also to polymers containing NH-CH2-CH2NH units and other alkylenediamine units (e.g. NH-CH)2-CH2-CH2-NH units, NH-CH2-CH(CH3) -NH Unit, NH- (CH)2)4-NH Unit, NH- (CH)2)6-NH Unit or NH- (CH)2)8-NH Unit) of a polyalkyleneimine, with the proviso that NH-CH2-CH2The molar proportion of-NH units is predominant. Preferred polyethyleneimines contain a majority of NH-CH relative to the molar proportion2-CH2-NH units, for example 60 mol% or more in total, more preferably at least 70 mol% in total, relative to all alkylenimine units. In a particular embodiment, the term polyethyleneimine means a polyethyleneimine containing one or zero NH-CH per polyethyleneimine structural unit2-CH2-those polyethyleneimine having alkyleneimine units other than NH.
In the context of the present invention, the term "polypropyleneimine" refers not only to polypropyleneimine homopolymers, but also to homopolymers containing NH-CH2-CH(CH3) NH units and other alkylenediamine units (e.g. NH-CH)2-CH2-CH2-NH units, NH-CH2-CH2-NH Unit, NH- (CH)2)4-NH Unit, NH- (CH)2)6-NH Unit or NH- (CH)2)8-NH Unit) of a polyalkyleneimine, with the proviso that NH-CH2-CH(CH3) The molar proportion of-NH units is predominant. Preferred polypropyleneimines contain a majority, relative to the molar proportion, of NH-CH2-CH(CH3) -NH units, for example 60 mol% or more in total, more preferably at least 70 mol% in total, relative to all alkylenimine units. In a particular embodiment, the term polypropyleneimine refers to a structure containing one or zero NH-CH per polypropyleneimine structural unit2-CH(CH3) -those polyalkyleneimines of alkyleneimine units other than NH.
The polyalkyleneimine structural units are preferably branched, more preferably highly branched. The branch may be an alkyleneamino group, such as but not limited to-CH2-CH2-NH2Radical or (CH)2)3-NH2-a radical. The longer branch may be, for example, - (CH)2)3-N(CH2CH2CH2NH2)2Or- (CH)2)2-N(CH2CH2NH2)2And (4) a base.
Highly branched polyethyleneimines are, for example, polyethyleneimine dendrimers or related molecules having a Degree of Branching (DB) in the range from 0.25 to 0.95, preferably in the range from 0.30 to 0.80, particularly preferably from 0.5 to 0.7, most preferably from 0.60 to 0.65.
These hyperbranched polymers are characterized by a Degree of Branching (DB), which represents the percentage of dendritic and terminal monomers among all the monomers in the polymer: the degree of branching can be determined, for example, by13C-NMR or15N-NMR spectroscopy, preferably at D2O, and is defined as follows:
DB＝(D+T)/(D+T+L)
where D (dendritic) corresponds to the fraction of tertiary amino groups, L (linear) corresponds to the fraction of secondary amino groups, and T (terminal) corresponds to the fraction of primary amino groups.
In the context of the present invention, CH3The basis is not considered a branch.
In one embodiment of the present invention, the substrate is,the weight-average molecular weight (M) of the polyalkyleneimine structural units, preferably of the polyethyleneimine or polypropyleneimine structural unitsw) At about 430g/mol to about 4.3 x 106g/mol, preferably in the range of about 500g/mol to about 2 x 106g/mol, more preferably in the range of about 800g/mol to about 2 x 106g/mol, even more preferably in the range of about 800g/mol to about 2 x 105In the range of g/mol, most preferably from about 800g/mol to 2 x 104The weight average molecular weight (Mw) of the polyalkyleneimine unit can be determined by Gel permeation chromatography-light Scattering (Gel Permationchromatography-L light Scattering; GPC-L S) of each polyalkyleneimine.
Polyalkyleneimines, and in particular polyethyleneimines, suitable for the purposes of the present invention can be commercially available or obtained by known methods by those skilled in the art. Suitable methods for preparing branched polyethyleneimines are known. For example, polyethyleneimines can be prepared, for example, by ring-opening polymerization of aziridines, which has been developed for a relatively long time, as has been described, for example, in Advances in the Chemistry of polyethylenimine (Polyaziridine), Zhuk, D.S., Gembitskii, P.A., and Kargin V.A., Russian Chemical Reviews, volume 34(7), 515-526, 1965.
In one particular embodiment of the invention, for example, the polyethyleneimine structural unit may have a composition represented by the following general formula: - (CH)2-CH2-NH)-mWherein m is more than or equal to 10 and less than or equal to 105Preferably 10. ltoreq. m.ltoreq.104More preferably 10. ltoreq. m.ltoreq.103Most preferably 10. ltoreq. m.ltoreq.100, for example 10. ltoreq. m.ltoreq.50.
The polysiloxane structural units (ii) contained in the copolymer according to the invention are derived from epoxy-terminated polysiloxanes having the structure of formula (I):
wherein
R1、R2、R3And R4Independently of one another are hydrogen, C1-C4Alkyl or C1-C4An alkoxy group; r5And R6Independently of one another are hydrogen, C1-C4Alkyl radical, C1-C4Alkoxy or
Wherein G is C1-C20Alkylene, preferably C1-C8Alkylene, which is optionally interrupted by O and represents a link to the remainder of the molecule, with the proviso that R5And R6At least one is an epoxy group or has an epoxy group at a terminal, and n is in the range of 1 to 90, preferably in the range of 1 to 80, more preferably in the range of 4 to 70, for example 4 to 60.
In one embodiment of the epoxy-terminated polysiloxane having the structure of formula (I), R5And R6At least one of which is a group of formula (II):
wherein
w is a variable in the range of 1 to 10, preferably 1 to 6, more preferably 1 to 4, and refers to the number of ethylene repeating units,
R7is H or C1-C4Alkyl, preferably H and methyl, and
denotes the linkage to the rest of the structure of the molecule.
The polysiloxane structural units (ii) of the copolymers of the invention, epoxy-terminated polysiloxanes derived therefrom, can be prepared by the skilled person according to known methods. Methods for producing epoxy-terminated polysiloxanes are known in the art. For example, epoxy-terminated polysiloxanes can be commercially available or can be prepared by, for example, Synthesis of epoxy-capped silicones, ZHU Hong et al, Textile Autoliaries, p18-20, No.8, Vol.32, 2015; or Synthesis of Epoxy Modified methyl methacrylate and Application of the Same, DU Xiiaopeng et al, Silicone materials, 32-36,22(1): 2008.
The copolymers of the invention can be prepared by polymerizing a monomer mixture containing on average at least 10 polymerized C2-C10-polyalkyleneimine of alkyleneimine units is reacted with an epoxy-terminated polysiloxane. Any of the preferred choices for polyalkyleneimines and epoxy-terminated polysiloxanes as described above can be applied here. In this reaction, the epoxy group of the epoxy-terminated polysiloxane reacts with the hydrogen atom of the amino group in the polyalkyleneimine to obtain the copolymer of the present invention.
For example, the reaction of the polyalkyleneimine with the epoxy-terminated polysiloxane can be carried out at a temperature in the range of 10 ℃ to 90 ℃, more preferably 20 ℃ to 60 ℃, and most preferably at a temperature of about 50 ℃.
The pressure at which the reaction is carried out is not particularly limited, and is, for example, 1atm to 5atm, preferably 1 atm.
In a particular embodiment according to the present invention, the reaction may be carried out at about 50 ℃ and 1 atm.
The reaction time is not particularly limited, and may be usually several hours, for example, 5 hours.
In a preferred embodiment, the copolymer of the invention is prepared by: the polyalkyleneimines as defined above are reacted with the epoxy-terminated polysiloxanes as defined above in the presence of an agent which can control the cross-linking between the polyalkyleneimines and the epoxy-terminated polysiloxanes, in particular in the case of epoxy-doubly terminated (epoxy-terminated) polysiloxanes, to provide water-soluble copolymers. Without wishing to be bound by any theory, such agents may act as a terminator that competes with the polyalkyleneimine in the reaction of the polyalkyleneimine with the epoxy-terminated polysiloxane. The agent is chosen, for example, from dialkanolamines, polyetherdiamines, the alkanol groups of which may be identical or different.
In a more preferred embodiment, the copolymer of the invention is prepared by: the polyalkyleneimine as defined above is reacted with the epoxy-terminated polysiloxane as defined above in the presence of an agent which can control the cross-linking between the polyalkyleneimine and the epoxy-terminated polysiloxane in a molar ratio of the polyalkyleneimine to the agent in the range of 1:1 to 10:1, more preferably 1.5:1 to 5: 1.
Suitable dialkanolamines include, but are not limited to, N-bis (2-ethanol) amine, N-bis (2-propanol) amine, N-bis (3-propanol) amine, N-bis (2-butanol) amine, N-bis (3-butanol) amine, N-ethanol-N- (2-propanol) amine, N- (2-ethanol) -N- (2-butanol) amine, and N- (2-propanol) -N- (2-butanol) amine. N, N-di (2-ethanol) amine or diethanolamine are preferred.
Suitable polyetherdiamines include, but are not limited to, those having the structure of formula (III):
wherein
R8Is H or methyl, preferably methyl;
R9is H or methyl, preferably methyl; and is
x is such that the polyether diamine has a weight average molecular weight (M)w) A number in the range of 200 to 4000, preferably 230 to 2000.
Examples of polyether diamines include those available from Hensman Corporation (Huntsman Corporation), Shanghai, China
D230、
D400、
D2000。
In a preferred embodiment of the invention, an excess of polyalkyleneimine is used for the reaction per mole of epoxy-terminated polysiloxane, so that all epoxy-terminated polysiloxanes in the reaction system will be linked to the polyalkyleneimine and there are remaining free amino groups, especially primary and secondary amino groups. Overall, the molar equivalent ratio of epoxy-terminated polysiloxane to primary amino groups of polyalkyleneimine is in the range of 1:1 to 1:40, preferably the molar ratio of epoxy-terminated polysiloxane to primary amino groups of polyalkyleneimine is in the range of 1:5 to 1:30, more preferably the molar ratio of epoxy-terminated polysiloxane to primary amino groups of polyalkyleneimine is in the range of 1:10 to 1:20 for the reaction.
In particular, copolymers of polyethyleneimine with epoxy-terminated polysiloxanes are used in combination with the immobilizing agent in the present invention. As described further below, this fixative is preferably selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine, and dialdehydes.
A second aspect of the present invention relates to a textile softening composition comprising:
(A) at least one copolymer according to the invention as described above for the first aspect of the invention as a textile softener.
Preferably, the textile softening composition, when actually applied for textile treatment, contains from 0.1 to 5 wt%, preferably from 0.2 to 2 wt% of component (a). The textile softening composition may be in the form of an aqueous solution or a concentrate that will be diluted to the desired concentration prior to softening the textile. The concentrate may contain component (a), for example, in the range of 10 to 50 wt%, preferably 15 to 40 wt%, more preferably 15 to 20 wt%, and may then be diluted with water before application.
In the case of an aqueous solution or concentrate, the textile softening composition of the present invention can contain high levels of water in an amount of at least about 50%, preferably at least about 60%, and more preferably at least about 70%, based on the total weight of the textile softening composition.
In the case of aqueous solutions or concentrates, the textile softening compositions of the present invention may also contain solvents other than water. Solvents are suitable for fluidizing the textile softening compositions of the present invention and can provide good dispersibility, and in some embodiments, transparent or translucent compositions. Solvents suitable for use in the present invention may be water soluble or water insoluble. Non-limiting examples of solvents include ethanol, propanol, isopropanol, n-propanol, n-butanol, t-butanol, propylene glycol, 1, 3-propanediol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2, 3-propanetriol, propylene carbonate, phenethyl alcohol, 2-methyl-1, 3-propanediol, hexylene glycol, glycerol, butyldiglycol sorbitol, polyethylene glycol, 1, 2-hexanediol, 1, 2-pentanediol, 1, 2-butanediol, 1, 4-cyclohexanedimethanol, tetramethylethylene glycol, 1, 5-hexanediol, 1, 6-hexanediol, 2, 4-dimethyl-2, 4-pentanediol, 2, 4-trimethyl-1, 3-pentanediol (and ethoxylates thereof), 2-ethyl-1, 3-hexanediol, phenoxyethanol (and ethoxylates thereof); glycol ethers such as butyl carbitol and dipropylene glycol n-butyl ether; ester solvents such as dimethyl esters of adipic acid, glutaric acid, and succinic acid; hydrocarbons such as decane and dodecane; or any combination thereof. In one embodiment, the composition is free or substantially free of the above-described solvent.
The textile softening composition of the present invention may further comprise a surfactant. Surfactants are emulsifiers for the textile softener and can also help disperse the composition during the treatment process. Suitable surfactants may include nonionic surfactants, such as C12-C18Alkyl ethoxylates, e.g. from Shell (Shell)
A nonionic surfactant; cationic surfactants such as Alkoxylated Quaternary Ammonium (AQA) surfactants; zwitterionic surfactants, such as betaines, e.g., alkyl dimethyl betaine and coco dimethyl amidopropyl betaine; amphoteric surfactants, such as aliphatic derivatives of secondary or tertiary amines; and mixtures thereof.
Preferably, the textile softening composition of the present invention may further comprise a nonionic surfactant.
The textile softening compositions of the present invention may also contain other additives.
Additional additives suitable for use in textile softening compositions can be incorporated into the textile softening compositions of the present invention by those skilled in the art depending on the application.
Preferably, the textile softening compositions of the invention containing (a) the copolymers according to the invention can be used in combination with (B) a fixing agent.
The fixative is preferably selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehydes.
Without wishing to be bound by any particular theory, it is believed that the fixing agent is effective in improving the attachment of the copolymer according to the invention, for example by crosslinking the fibrous material of the textile or forming a three-dimensional network with the copolymer according to the invention. By fixing the copolymers according to the invention with a fixing agent, the textile softening compositions can provide the desired softening effect, in particular a soft and fluffy hand, for a long time, even after several rinses of the textile or several washes.
Dialdehydes suitable for use as component (B) of the textile softening composition of the present invention may have from 2 to 15 carbon atoms, preferably from 2 to 10 carbon atoms, and more preferably from 2 to 8 carbon atoms, for example glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde and adipaldehyde, most preferably glyoxal and glutaraldehyde.
When both component (a) and component (B) are applied for textile treatment, the weight ratio of component (a) to component (B) is in the range of 50:1 to 1:10, more preferably 20:1 to 1: 1. For example, in a preferred embodiment of the present invention, the weight ratio of component (a) to component (B) is in the range of from 20:1 to 6:1, more preferably from 10:1 to 6: 1.
In general, when actually applied to textile treatment, component (B) is applied in the form of a solution. Water is preferred as the solvent for the solution of fixative. There is no particular limitation on the concentration of the fixing agent in the solution, as long as an effective amount of fixing agent is available to improve the attachment of component (a), the copolymer of the present invention, to the textile. The amount of fixing agent will depend on the component (a) to be left on the textile and can be adjusted by controlling the concentration of fixing agent and/or the period of treatment with fixing agent. The concentration of the fixing agent in the solution is desirably in the range of 0.01 wt% to 0.1 wt%.
A third aspect of the present invention is a process, especially an industrial process, for treating a textile comprising the step of treating the textile with a solution of a textile softening agent selected from the copolymers of the present invention, especially the textile softening composition of the present invention. The step of treating the textile is not particularly limited and may be accomplished by, for example, dipping, spraying, printing and/or plating (plating). Preferably, the textile is impregnated with the solution of textile softener by immersing the textile into or passing the textile through the solution of textile softener. Preferably, the process for treating the textile according to the invention is an exhaust process or a padding process.
In a preferred embodiment, the method for treating textiles according to the invention comprises further treating the textile loaded with a textile softener by a fixing agent selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehyde. The dialdehyde is preferably selected from glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde or adipaldehyde, more preferably from glyoxal or glutaraldehyde.
Thus, a preferred method for treating a textile according to the invention comprises
a) Treating the textile with a solution of a textile softener selected from the copolymers of the present invention to obtain a substrate loaded with the textile softener;
b) optionally, removing any excess softener from the textile loaded with the textile softener; and
c) the textile loaded with textile softening agent is further treated by a fixing agent selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and a dialdehyde, wherein the dialdehyde is preferably selected from glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde or adipaldehyde, more preferably from glyoxal or glutaraldehyde.
It is to be understood that all features and corresponding preferred choices described above for the textile softener (i.e. the copolymer of the invention) and the fixing agent may be applied accordingly to the method for treating the textile of the invention according to the third aspect.
In a preferred embodiment in which the textile softener is impregnated onto the textile, the textile is immersed into or passed through a solution of the textile softener, typically an aqueous solution of the textile softener. There is no particular limitation on the concentration of the textile softener in the solution, as long as an effective amount of the textile softener can be loaded into the final textile. Overall, the concentration of the textile softener in the solution is in the range of 0.1 to 5 wt.%, preferably 0.2 to 2 wt.%.
The solution of textile softener may further contain additional additives in conventional amounts commonly used in textile softening compositions. Such additives include, but are not limited to, additional solvents, surfactants, and the like. All features and corresponding preferences described above for the further additives can be applied here accordingly.
The removal may typically be achieved by passing the textile loaded with the textile softener through an apparatus comprising one or more rolls to leave the desired amount of textile softener on the textile, any apparatus containing one or more rolls may be used for this purpose, such as a kiss roll (kiss roll) or a Padding machine (foamed).
The pressing force will depend on the amount of textile softener to be left in the final material, on the concentration of the solution and/or on the type of textile to be treated and the water content. In general, a pressing force of 0.5 to 6 bar may be used, preferably a pressure of 2 to 4 bar is applied.
Steps a) and b) can be carried out at any suitable temperature that does not alter the properties of the textile and textile softener. Preferably, steps a) and b) are carried out at room temperature (e.g. 23 ℃).
In step c), if step b) is carried out, the textile loaded with textile softener obtained from step a) or step b) is subjected to a fixative treatment. The treatment in step c) may be achieved by any suitable means of introducing the fixing agent into the textile loaded with textile softening agent obtained from step a) or step b) (if step b) is performed, for example by dipping or spraying.
According to a preferred embodiment of introducing the fixing agent into the textile loaded with the textile softener by impregnation, the textile is immersed into or passed through a solution of the fixing agent, typically an aqueous solution of the fixing agent. The treatment with the fixing agent is generally carried out at a temperature in the range of 10 ℃ to 50 ℃, preferably 15 ℃ to 30 ℃, and more preferably 20 ℃ to 25 ℃. There is no particular limitation on the concentration of the fixing agent in the solution, as long as an effective amount of the fixing agent can be used to fix the textile softener to the textile. The amount of fixing agent will depend on the textile softener to be left on the final material and can be adjusted by controlling the concentration of fixing agent and/or the period of time of treatment with fixing agent. The concentration of the fixing agent in the solution is desirably 0.01 wt% to 0.1 wt%.
As described above for the second aspect of the invention, the textile softening agent and the fixing agent are preferably comprised in the final textile in a weight ratio in the range of from 50:1 to 1:10, more preferably from 20:1 to 1:1, still more preferably from 12:1 to 6: 1. For example, in a preferred embodiment of the present invention, the weight ratio of textile softener to fixative is in the range of 20:1 to 6:1, more preferably 10:1 to 6: 1.
In a particular embodiment, the method for treating textiles according to the invention further comprises a step d) to dry the textile that has been treated with the fixing agent in step c).
In step d), the textile that has been treated with the fixing agent is dried for a period of time, preferably in an oven, at a temperature in the range of 100 ℃ to 220 ℃, preferably 120 ℃ to 170 ℃, the period of drying time depending on the amount of textile softener, fixing agent and water present in the textile, on the type of textile to be treated, on the temperature and/or efficiency of the drying system.
The method of treating a textile according to the invention can be carried out continuously, i.e. the textile is subjected to the incorporation of textile softener (e.g. by impregnation), the optional removal of any excess textile softener (e.g. by pressing), the treatment with fixing agent (e.g. by impregnation), and drying without any intermediate stages or pauses.
Textiles suitable for treatment with the textile softening compositions of the present invention may be prepared from various natural or synthetic fibers, such as woven (woven fabric), knitted (knit fabric) or nonwoven (nonwoven fabric), for example, the textiles may be prepared from natural fibers (e.g., cotton) or synthetic fibers, such as polyesters (e.g., polyethylene terephthalate; PET), polyglycolide or polyglycolic acid; PGA), polylactic acid (poly lactic acid; P L a), polycaprolactone (polycaprolactone; PC L), polyhydroxyalkanoates (polyhydroxyalkanoates; PHA), polyhydroxybutyrates (polyhydroxybutyrates; polyethylene adipates; PEA), polybutylene succinates (polybutylene succinates; polyhydroxybutyrates; poly (3-hydroxybutyrate-3-polyhydroxybutyrate), poly (polyhydroxybutyrate; poly (3-hydroxy-3-phthalate; poly (3-polytrimethylene naphthalate; poly (styrene-3-naphthalate; poly (styrene-co-3-polyethylene naphthalate; poly (3-propylene), poly (polyhydroxybutyrate; poly (styrene-3-naphthalate; poly (trimethylene-terephthalate; poly (trimethylene-3-terephthalate), etc.), poly (trimethylene terephthalate), poly (trimethylene-3-naphthalate; poly (trimethylene-terephthalate; etc.), poly (trimethylene-naphthalate, etc.).
For example, the copolymers of the present invention may be applied to PE/PP or PE/polyester (e.g., PE/PET) bicomponent nonwovens made of continuous filament fibers and not or very little napped, and comprising a Polyethylene (PE) sheath and made of polypropylene (PP) or polyester (e.g., polyethylene terephthalate; PET), polyglycolide or polyglycolic acid; PGA), polylactic acid (P L A), polycaprolactone (PC L), polyhydroxyalkanoate (polyhydroxyalkanoate; PHA), polyhydroxybutyrate (polyhydroxybutyrate; polyhydroxybutyrate), polyethylene adipate (polyethylene adipate; PEA), polybutylene succinate (polybutylene succinate; polybutyrate-3-Polyhydroxybutyrate) (PHB), polyethylene naphthalate (3-polytrimethylene terephthalate), polyethylene terephthalate (polyethylene terephthalate.
A fourth aspect of the present invention is the use of the copolymers of the invention for textile softening in the textile industry, in particular during textile finishing steps in the textile industry. In particular, the present invention relates to the use of the copolymers of the invention in combination with a fixing agent for prolonging the soft feel of textiles. As described above, this fixative is preferably selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehyde, wherein the dialdehyde is preferably selected from glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde or adipaldehyde, more preferably from glyoxal or glutaraldehyde.
A fifth aspect of the invention is a textile softening kit comprising
(A) As a textile softening agent, a copolymer according to the invention as described above for the first aspect of the invention, or a textile softening composition as described above for the second aspect of the invention; and
(B) a fixative selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehyde,
wherein in the textile softening kit the textile softener and the fixing agent are filled separately from each other.
It is to be understood that all features and corresponding preferred choices described above for the textile softener (i.e. the copolymer of the invention) and the fixing agent may be applied accordingly to the textile softening kit according to the fifth aspect.
The textile softener and fixative can be contained in different packages or in different parts of a single package so that they do not mix during storage or delivery.
In a sixth aspect, the present invention relates to a waterproofing composition comprising:
(A) at least one copolymer according to the invention as described above for the first aspect of the invention acts as a water repellent.
Preferably, the water-repellent composition contains from 0.1 to 5% by weight, preferably from 0.2 to 2% by weight, of component (a) when actually applied in textile treatment. The waterproofing composition may be in the form of an aqueous solution or a concentrate that is diluted to the desired concentration prior to textile treatment. The concentrate may contain component (a), for example, in the range of 10 to 50 wt%, preferably 15 to 40 wt%, more preferably 15 to 20 wt%, and may then be diluted with water before application.
In the case of aqueous solutions or concentrates, the waterproofing compositions of the present invention can contain high levels of water in an amount of at least about 50%, preferably at least about 60%, and more preferably at least about 70%, based on the total weight of the waterproofing composition.
In the case of aqueous solutions or concentrates, the waterproofing compositions of the invention may also contain solvents other than water. Suitable solvents for use in the waterproofing composition include those described above in the second aspect. In one embodiment, the composition is free or substantially free of the above-described solvent.
The waterproof composition of the present invention may further contain a surfactant and/or other conventional additives. Surfactants are emulsifiers for water repellents and may also help disperse the composition during the treatment process. Suitable surfactants may include nonionic surfactants, such as C12-C18Alkyl ethoxylates, e.g. from Shell (Shell)
A nonionic surfactant; cationic surfactants, such as Alkoxylate Quaternary Ammonium (AQA) surfactants; zwitterionic surfactants, such as betaines, e.g., alkyl dimethyl betaine and coco dimethyl amidopropyl betaine; amphoteric surfactants, such as aliphatic derivatives of secondary or tertiary amines; and mixtures thereof.
Preferably, the waterproof composition of the present invention may further contain a nonionic surfactant.
Further additives suitable for use in the waterproofing composition may be incorporated into the waterproofing composition of the present invention by those skilled in the art depending on the actual application.
Preferably, the waterproofing composition of the present invention containing (a) the copolymer according to the present invention can be used in combination with (B) a fixing agent.
The fixative is preferably selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehydes. Suitable fixing agents for use in the waterproofing composition include those described in the above aspects.
Preferred embodiments of the water repellent composition are the same or similar to the embodiments of the textile softening composition described above. All features and corresponding preferred choices are the same or similar to those described above for the textile softening composition.
In a seventh aspect, the present invention relates to a process, especially an industrial process, for treating textiles, comprising the step of treating the textiles with a solution of a water repellent agent selected from the copolymers of the present invention, especially the water repellent composition of the present invention. The step of treating the textile is not particularly limited and may be accomplished by, for example, dipping, spraying, printing, and/or plating. Preferably, the textile is impregnated with the solution of the water repellent agent by immersing the textile in or passing the textile through the solution of the water repellent agent. Preferably, the process of the invention for treating textiles is an exhaust process or a padding process.
In particular, the present invention relates to an industrial process for treating a textile, comprising: a first step of contacting it with a waterproofing composition comprising the copolymer of the present invention; and in a second step contacting the textile with a fixing agent.
The fixative is preferably selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehydes.
Preferred methods of treating textiles by using the waterproofing composition are the same or similar to those methods of treating textiles with textile softening compositions. All features and corresponding preferred choices are the same or similar to those described above for the textile treatment process utilizing the textile softening composition.
Examples
The present invention will be further described below with reference to specific embodiments, which are exemplary and explanatory only and are not limiting.
The following materials were used in the preparation methods described below. When parts and percentages are used, they are provided by weight unless otherwise defined.
The materials used were:
preparation examples
Example 1: production of copolymer-1 of the present invention
Mixing Polyethylenimine-8h (23g),
D230(3.99g) and isopropanol (i-PrOH) (40g) were placed in a reactor and heated to a temperature of 50 ℃. Epoxy-terminated Polysiloxane (42.79g, Polysiloxane, Yound, YD-830) dissolved in i-PrOH (50g) was added dropwise to the reactor at 50 ℃. The reaction was kept at the same temperature for another 1h and then the solvent i-PrOH was carefully distilled off.
The resulting product was copolymer-1 having the composition shown in table 1:
TABLE 1
| Copolymer-1 | Polyethylene imine | Epoxy-terminated polysiloxanes | Jeffamine D230 |
| wt[％] | 33 | 61 | 6 |
Example 2: production of copolymer-2 of the present invention
Step I: epoxy-terminated Polysiloxane (42.8g, Polysiloxane, you d, YD-830), diethanolamine (1.17g), and i-PrOH (50g) were added to reactor No. 1, respectively, at a temperature of about 50 ℃, and then stirred at the same temperature for 30 minutes after the addition. The solution obtained from the reaction in this step was used in step II.
Step II: polyethylene imine-8h (23g) and i-PrOH were placed in reactor No. 2 to form a PEI solution. The solution prepared in step I is metered into the PEI solution. The reaction was heated to a temperature of up to about 50 ℃ and held at that temperature for 2.5h to complete the reaction.
The resulting product was copolymer-2 having the composition shown in table 2:
TABLE 2
| Copolymer-2 | Polyethylene imine | Epoxy-terminated polysiloxanes | Diethanolamine (DEA) |
| wt[％] | 34 | 64 | 2 |
Example 3: production of copolymer-3 of the present invention
Step I: epoxy-terminated Polysiloxane (20.5g, Polysiloxane, Yound, YD-830), diethanolamine (0.56g), and i-PrOH (50g) were added to reactor No. 1, respectively, at a temperature of about 50 ℃, and then stirred at the same temperature for 30 minutes after the addition to complete the reaction. The solution obtained from the reaction in this step was used in step II.
Step II: polyethylene imine-13h (23g) and i-PrOH (40g) were added to reactor No. 2 to form a PEI solution. The solution prepared in step I is metered into the PEI solution. The reaction was heated to a temperature of up to about 50 ℃ and held at that temperature for 2.5h to complete the reaction.
The resulting product was copolymer-3 having the composition shown in table 3:
TABLE 3
| Copolymer-3 | Polyethylene imine | Epoxy-terminated polysiloxanes | Diethanolamine (DEA) |
| wt[％] | 52 | 47 | 1 |
Example 4: production of copolymer-4 of the present invention
Step I: epoxy-terminated Polysiloxane (20.54g, Polysiloxane, you nd, YD-830), diethanolamine (0.56g), and i-PrOH (50g) were added to reactor No. 1at a temperature of about 50 deg.C, and then stirred for 30 minutes to complete the reaction. The solution obtained from the reaction in this step was used in step II.
Step II: polyethylene imine-20h (23g) and i-PrOH (40g) were placed in reactor No. 2 to form a PEI solution. The solution prepared in step I is metered into the PEI solution. The reaction was heated to a temperature of up to about 50 ℃ and held at that temperature for 2.5h to complete the reaction.
The resulting product was copolymer-4 having the composition shown in table 4:
TABLE 4
| Copolymer-4 | Polyethylene imine | Epoxy-terminated polysiloxanes | Diethanolamine (DEA) |
| wt[％] | 52 | 47 | 1 |
In example 1
D230 and diethanolamine of examples 2 to 4, respectively, were used as agents to control the crosslinking between Polyethyleneimine (PEI) and epoxy-terminated polysiloxane during the synthesis of the copolymer, to avoid the formation of water-insoluble polymers。
Working examples
Each of copolymers 1 to 4 and comparative hydrophilic silicone oil textile softener products according to the invention and prepared as above were applied during padding (padding) and evaluated for each efficacy in improving hand by grading.
The following commercially available materials were tested as comparative products.
| Material | Description of the invention | Suppliers of goods |
| TF405B | Hydrophilic silicone oil | TRANSFAR INTERNATIONA L CORP, Zhejiang, China |
The padding process is performed as follows.
A piece of Cotton knitted fabric (Cotton knit fabric) was immersed in a bath containing 4g/l of an aqueous solution of a softener at a pH value of 4.5 adjusted by acetic acid, then passed through a roll at a pressure of 4 bar and an upper loading rate of 100% (the upper loading rate is an amount calculated according to the following formula: the upper loading rate ═ weight of fabric passed through the roll-initial weight of fabric)/initial weight of fabric), then dried in an oven at 160 ℃ for 120 seconds, and equilibrated at a temperature of 20 ℃ and a humidity of 65% for 2 hours.
The softness of the treated fabric samples was measured by hand feel and rated as follows:
"5": preferably, the amount of the organic solvent to be used,
"4": it is very good that the air conditioner is provided with,
"3": it is preferable that the content of the first component,
"2": poor, and
"1": the worst.
The test results are provided in table 5 below.
To test the wash durability of the textile softeners of the present application after one or more wash cycles, after one wash (1) and after five washes (5), the textile materials were further evaluated according to the wash standard GB/T8629-2001 ("textile-home washing and drying procedure for textile testing)", equivalent to ISO 6330: 2000). The results are also given in table 5 below.
Fixing process
After the padding process, fixing (fixing) is performed in the same padding machine to improve the durability of the softener on the fabric.
A piece of cotton knitted fabric was dipped into a bath containing 4g/l of a softener at a pH value of 4.5 adjusted by acetic acid, and then passed through a roller at a pressure of 4 bar and an upper loading rate of 100% (the upper loading rate is an amount calculated according to the following formula: upper loading rate ═ weight of fabric passed through roller-initial weight of fabric)/initial weight of fabric). The fabric was allowed to dry at 120 ℃ for 180 seconds. The fabric was then immersed in a bath containing 0.2g/l of an aqueous solution of glutaraldehyde for 3 seconds, removed, dried in an oven at 120 ℃ for 120 seconds, and equilibrated at 25 ℃ and 65% humidity for 2 hours.
The process parameters are provided below.
TABLE 5 softness and durability efficacy
1: the term "blank" means that the fabric is tested as is without any treatment.
Water resistance test
Copolymer 2, comparative hydrophilic silicone oil textile treatment product, and initial feedstock YD-830, prepared in accordance with the invention and as described above, were applied during the pad-soak process/fixturing process and evaluated for their respective effectiveness in improving water repellency the pad-soak process and fixturing process were the same as described above except that the test fabric was immersed in a bath containing 4g/L of the textile treatment in aqueous solution as the water repellent.
The evaluation of the Water Repellency of textile fabrics was carried out according to AATCC 222010, EN 24920 (Spray-test dynamic Water Repellency 100-Point Testing Scale). The test results are provided in table 6 below.
Test program
The test fabric was securely fastened in a 150mm diameter hoop so that the face of the test fabric would be exposed to the water spray. The surface of the fabric should be smooth and wrinkle-free. The hoops were placed on the tester's stand at 45 ° to the uppermost fabric in a position such that the center of the spray pattern coincided with the center of the hoop. The distance should be 150 mm.
250ml of distilled water was poured into the funnel of the tester at a temperature of 27 ℃ and allowed to spray onto the test fabric for 25 to 30 seconds. After shaking off the remaining droplets, the wetting or dot pattern was compared to the grade map.
The efficiency of water repellency is graded on a 6-scale of 0, 50, 70, 80, 90, and 100.
Spray rating of 100 means no dripping (sticking) or wetting of the upper surface (optimal water resistance).
The spray rating of 90 means a slight random tack or wetting of the upper surface.
Spray rating 80 means that the upper surface is wetted at the spray point.
Spray rating 70 means that the entire upper surface is partially wetted.
Spray rating 50 means complete wetting of the entire upper surface.
Spray rating 0 means complete wetting of the entire upper and lower surfaces.
TABLE 6 Water repellency Performance
| Sample (I) | Water-proof property |
| YD-830 | 50 |
| Hydrophilic silicone oil emulsion TF405B | 0 |
| Copolymer-2 | 90 |
| Copolymer-2 and fixative | 80 |
| Blank space | 0 |
The term "blank" means that the fabric is tested as is without any treatment.
Claims (28)
1. A copolymer comprising the following structural units per molecule:
(i) at least one polyalkyleneimine structural unit containing an average of at least 10 polymerized C2-C10-an alkylenimine unit, and
(ii) at least one polysiloxane structural unit derived from an epoxy-terminated polysiloxane,
it is used as a textile softener in the textile industry.
2. The copolymer according to claim 1, wherein the polyalkyleneimine structural units (i) are polyethyleneimine or polypropyleneimine structural units.
3. The copolymer according to claim 1 or 2, wherein the polysiloxane structural unit (ii) is derived from an epoxy-terminated polysiloxane having the structure of formula (I):
wherein
R1、R2、R3And R4Independently of one another are hydrogen, C1-C4Alkyl or C1-C4An alkoxy group;
R5and R6Independently of one another are hydrogen, C1-C4Alkyl radical, C1-C4Alkoxy radicals or radicals
Wherein G is C optionally interrupted by O1-C8Alkylene and represents a link to the rest of the molecule, with the proviso that R5And R6At least one of which is an epoxy group or has an epoxy group at a terminal, and
n is in the range of 1 to 90, preferably in the range of 1 to 80, more preferably in the range of 4 to 70, for example 4 to 60.
4. The copolymer of any one of claims 1 to 3, prepared by polymerizing a monomer mixture comprising on average at least 10 polymerized C2-C10-polyalkyleneimine of alkyleneimine units is reacted with an epoxy-terminated polysiloxane.
5. The copolymer according to any one of claims 1 to 4, wherein the epoxy-terminated polysiloxane is an epoxy double-terminated polysiloxane.
6. The copolymer of claim 5 which has been prepared by polymerizing a monomer mixture containing an average of at least 10 polymerized C's in the presence of an agent selected from dialkanolamines in which the alkanol groups may be the same or different or from polyetherdiamines2-C10-polyalkyleneimine of alkyleneimine units is reacted with an epoxy-terminated polysiloxane.
7. The copolymer according to any one of claims 1 to 6, wherein the molar equivalent ratio of epoxy-terminated polysiloxane to primary amine groups of the polyalkyleneimine is in the range of 1:1 to 1:40, preferably 1:5 to 1:30, more preferably 1:10 to 1: 20.
8. The copolymer according to any one of claims 1 to 7, which is used as a water repellent in the textile industry.
9. A textile softening composition comprising a copolymer according to any of claims 1 to 7 as a textile softener.
10. The textile softening composition of claim 9, further comprising a surfactant.
11. A method for treating a textile comprising the step of treating the textile with a solution of a textile softener selected from the copolymers of any one of claims 1 to 7.
12. A method for treating a textile according to claim 11, wherein the copolymer according to any of claims 1 to 7 is applied by dipping, spraying, printing and/or plating.
13. The method for treating a textile according to claim 11 or 12, wherein after applying the copolymer according to any one of claims 1 to 7, the textile is treated with a fixative selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehyde.
14. A method for treating a textile according to claim 13, wherein the fixing agent is a dialdehyde having 2 to 15 carbons, preferably 2 to 10 carbons and more preferably 2 to 8 carbons.
15. A method for treating a textile according to claim 13, wherein the fixing agent is a dialdehyde selected from the group consisting of glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, and adipaldehyde, most preferably glyoxal and glutaraldehyde.
16. A method for treating a textile according to claim 11, comprising
a) Treating the textile with a solution of a textile softener selected from the copolymer according to any one of claims 1 to 7 to obtain a substrate loaded with the textile softener;
b) optionally, removing any excess softener from the textile loaded with textile softener; and
c) the textile loaded with a textile softening agent is treated by a fixing agent selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehydes, wherein the dialdehydes have from 2 to 15 carbons, preferably from 2 to 10 carbons and more preferably from 2 to 8 carbons, such as glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde and adipaldehyde, most preferably glyoxal and glutaraldehyde.
17. Method for treating a textile according to any one of claims 13 to 16, wherein the weight ratio of the textile softening agent to the fixing agent is in the range of 50:1 to 1:10, more preferably 20:1 to 1:1, such as in the range of 20:1 to 6:1, more preferably 10:1 to 6: 1.
18. A method for treating a textile according to any of claims 11 to 17, wherein the textile is prepared from natural or synthetic fibres, such as woven, knitted or non-woven fabrics.
19. A method for treating a textile according to any of claims 11 to 18, wherein the copolymer according to any of claims 1 to 7 is used as a water repellent.
20. Use of a copolymer according to any one of claims 1 to 7 for treating textiles as a textile softener in textile manufacture.
21. Use according to claim 20, wherein the copolymer according to any one of claims 1 to 7 is used in combination with a fixative selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehyde.
22. Use according to claim 21, wherein the dialdehyde has from 2 to 15 carbons, preferably from 2 to 10 carbons and more preferably from 2 to 8 carbons, such as glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde and adipaldehyde, most preferably glyoxal and glutaraldehyde.
23. Use according to claim 21 or 22, wherein the weight ratio of the textile softener to the fixing agent is in the range of 50:1 to 1:10, more preferably 20:1 to 1:1, such as in the range of 20:1 to 6:1, more preferably 10:1 to 6: 1.
24. Use according to any one of claims 20 to 23, wherein the copolymer according to any one of claims 1 to 7 is used during textile finishing processes in textile manufacture.
25. Use according to any one of claims 20 to 24, wherein the copolymer according to any one of claims 1 to 7 is used as a water repellent to treat textiles in textile manufacture.
26. A textile softening kit comprising
(A) The copolymer according to any one of claims 1 to 7 as a textile softener, or a textile softening composition according to claim 8 or 9; and
(B) a fixative selected from the group consisting of Epichlorohydrin (ECH), trichlorotriazine and dialdehyde,
wherein the textile softener and the fixative agent are separate from each other.
27. The textile softening kit of claim 26, wherein the dialdehyde has from 2 to 15 carbons, preferably from 2 to 10 carbons and more preferably from 2 to 8 carbons, such as glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, and adipaldehyde, most preferably glyoxal and glutaraldehyde.
28. The textile softening kit according to claim 26 or 27, wherein the weight ratio of textile softener to fixative is in the range of 50:1 to 1:10, more preferably 20:1 to 1:1, such as in the range of 20:1 to 6:1, more preferably 10:1 to 6: 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017116177 | 2017-12-14 | ||
| CNPCT/CN2017/116177 | 2017-12-14 | ||
| PCT/CN2018/115646 WO2019114493A1 (en) | 2017-12-14 | 2018-11-15 | Copolymer of polyalkylenimine and polysiloxane and compositions con-taining the same |
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| Publication Number | Publication Date |
|---|---|
| CN111479855A true CN111479855A (en) | 2020-07-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201880079944.9A Pending CN111479855A (en) | 2017-12-14 | 2018-11-15 | Copolymers of polyalkyleneimines and polysiloxanes and compositions containing the same |
Country Status (3)
| Country | Link |
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| CN (1) | CN111479855A (en) |
| TW (1) | TW201930406A (en) |
| WO (1) | WO2019114493A1 (en) |
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| CN115976838A (en) * | 2023-02-14 | 2023-04-18 | 重庆交通大学 | Hydrophilic silicone oil composition and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58120879A (en) * | 1982-01-09 | 1983-07-18 | ミヨシ油脂株式会社 | Treating agent for synthetic fiber |
| JP2000178895A (en) * | 1998-12-11 | 2000-06-27 | Toppan Printing Co Ltd | Water-soluble functional compound, internally loading additive made of the same compound for papermaking, and paper loaded with the same additive |
| CN104508011A (en) * | 2012-07-27 | 2015-04-08 | 宝洁公司 | Consumer product compositions comprising organopolysiloxane conditioning polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108341956B (en) * | 2018-01-31 | 2021-03-05 | 杭州美高华颐化工有限公司 | Preparation method of universal type imine modified block organosilicon softener for polyester cotton |
-
2018
- 2018-11-15 WO PCT/CN2018/115646 patent/WO2019114493A1/en active Application Filing
- 2018-11-15 CN CN201880079944.9A patent/CN111479855A/en active Pending
- 2018-12-12 TW TW107144670A patent/TW201930406A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58120879A (en) * | 1982-01-09 | 1983-07-18 | ミヨシ油脂株式会社 | Treating agent for synthetic fiber |
| JP2000178895A (en) * | 1998-12-11 | 2000-06-27 | Toppan Printing Co Ltd | Water-soluble functional compound, internally loading additive made of the same compound for papermaking, and paper loaded with the same additive |
| CN104508011A (en) * | 2012-07-27 | 2015-04-08 | 宝洁公司 | Consumer product compositions comprising organopolysiloxane conditioning polymers |
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| TW201930406A (en) | 2019-08-01 |
| WO2019114493A1 (en) | 2019-06-20 |
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