CN104350199A - Treating solution for fibrous cellulosic material - Google Patents
Treating solution for fibrous cellulosic material Download PDFInfo
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- CN104350199A CN104350199A CN201280073886.1A CN201280073886A CN104350199A CN 104350199 A CN104350199 A CN 104350199A CN 201280073886 A CN201280073886 A CN 201280073886A CN 104350199 A CN104350199 A CN 104350199A
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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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/11—Compounds containing epoxy groups or precursors thereof
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
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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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
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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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- 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
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- 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
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Abstract
A treating solution for fibrous cellulosic material is provided. The treating solution comprises (A) an amino group functionalized organopolysiloxane, (B) an epoxy group functionalized organopolysiloxane, (C) a polycarboxylic acid, (D) an esterification catalyst, (E) an organic zirconium compound, (F) an emulsifier, and (G) water.
Description
Technical field
The present invention relates to the Treatment Solution of fibrous cellulosic materials.
Background technology
US 4820307 and US 4975209 discloses the Treatment Solution of cellulosic material, and it comprises polycarboxylic acids, curing catalysts and solvent.For improving the flexibility of the cellulosic fabric after process, US6582476 proposes a kind of formula comprising polycarboxylic acids, curing catalysts, carboxylic group functional polysiloxanes, surfactant and water.
But use this type for the treatment of compositions, the intensity of the process fabric of gained often dies down.
WO 2003/033807 discloses the finishing agent that one comprises crosslinked poly, curing agent, polycarboxylic acids, organosilicon softening agent (GE SM2112), surfactant and water.
But the intensity of the process fabric of gained is still inadequate.
Summary of the invention
The invention provides the novel process solution of fibrous cellulosic materials, it shows enough intensity, thus solves the technical barrier of this area.
The invention provides the Treatment Solution of fibrous cellulosic materials, it comprises:
(A) the functionalized organopolysiloxane of amino group,
(B) the functionalized organopolysiloxane of epoxide group,
(C) polycarboxylic acids,
(D) esterification catalyst,
(E) organic zirconate,
(F) emulsifying agent, and
(G) water.
In a preferred embodiment, this Treatment Solution also comprises (H) copolymer-maleic anhydride or the isocyanates through protection.
In another preferred embodiment, this Treatment Solution also comprises (I) polyalcohol.
In another preferred embodiment, the organopolysiloxane of component (A) and (B) is the polysiloxane represented by following averaged unit formula:
(R
3SiO
1/2)
a(XR
2SiO
1/2)
b(R
2SiO
2/2)
c(XRSiO
2/2)
d(RSiO
3/2)
e(XSiO
3/2)
f(SiO
4/2)
g
Wherein " a " represents the number of 0 to 50;
" b " represents the number of 0 to 50;
" c " represents the number of 30 to 2700;
" d " represents the number of 0 to 50;
" e " represents the number of 0 to 50;
" f " represents the number of 0 to 50;
" g " represents the number of 0 to 10;
" b+d+f " represents the number of 0.01 to 100;
" a+b+c+d+e+f+g " represents the number of 30 to 2700;
R represents monovalent hydrocarbon independently of one another, has the alkoxy base of 1 to 5 carbon atom or oh group; And
X represents the group being selected from amino group and epoxide group.
In another preferred embodiment, monovalent hydrocarbon comprises the alkyl group with 1 to 30 carbon atom, the aromatic yl group with 6 to 30 carbon atoms, has the alkenyl group of 2 to 30 carbon atoms and have the aromatic alkyl group of 7 to 30 carbon atoms.
In another preferred embodiment, amino group is the group be expressed from the next :-R
1-(NR
2cH
2cH
2)
l-NR
3r
4, wherein R
1represent the bivalent hydrocarbon radical with 1 to 30 carbon atom; R
2, R
3and R
4the group representing hydrogen atom, monovalent hydrocarbon, carboxyl groups independently of one another or be expressed from the next :-CH
2cH (OH) R
5, wherein R
5represent hydrogen atom, monovalent hydrocarbon or carboxyl groups; R
2, R
3and R
4in at least one be hydrogen atom; And l is the integer of 0 to 5.
In another preferred embodiment, epoxide group is selected from glycidoxyalkyl group group, epoxy cycloalkylalkyl group and oxiranylalkyl group group.
In another preferred embodiment, polycarboxylic acids is selected from: malic acid, oxo disuccinic acid, butanedioic acid, 1,2,3,4-BTCA, maleic acid, tricarballylic acid, citric acid, 1,2,3,4,5,6-cyclohexane hexacarboxylic acid, 1,2,3,4-cyclobutane tetrabasic carboxylic acid, propylene-1,2,3-tricarboxylic acids, 1,2,3,4-pentamethylene tetrabasic carboxylic acid, oxolane-2,3,4,5-tetrabasic carboxylic acid, 1,2,4-benzene tricarbonic acid, 1,2,4,5-benzene tertacarbonic acid and benzene hexacarboxylic acid.
In another preferred embodiment, esterification catalyst is selected from: carbodiimide, carboxylic acid, mineral acid, lewis acid and phosphorus oxyacid.
In another preferred embodiment, organic zirconate is selected from: four propyl alcohol zirconiums and four butanols zirconiums.
In another preferred embodiment, emulsifying agent is selected from: anion emulsifier, cationic emulsifier, amphoteric emulsifier and nonionic emulsifier.
Implement optimal mode of the present invention
The Treatment Solution of fibrous cellulosic materials of the present invention will be described in detail in following non-limiting part.
(A) the functionalized organopolysiloxane of amino group and the functionalized organopolysiloxane of (B) epoxide group
In the present invention, the component (A) of the Treatment Solution of fibrous cellulosic materials and (B) have the amino group of silicon bonding or the polysiloxane of epoxide group, are preferably the polysiloxane represented by following averaged unit formula:
(R
3SiO
1/2)
a(XR
2SiO
1/2)
b(R
2SiO
(/2)
c(XRSiO
2/2)
d(RSiO
3/2)
e(XSiO
3/2)
f(SiO
4/2)
g
In above formula, " a " represents 0 to 50, and is preferably 1 to 10, is more preferably 1 to 2;
" b " represents 0 to 50, and is preferably 0.01 to 10, is more preferably 0.1 to 5, is also preferably 0.5 to 2;
" c " represents 30 to 2700, and is preferably 60 to 1300, is more preferably 130 to 700;
" d " represents 0 to 50, and is preferably 0 to 5, is more preferably 0 to 1, is also preferably 0;
" e " represents 0 to 50, and is preferably 0 to 5, is more preferably 0 to 1, is also preferably 0;
" f " represents 0 to 50, and is preferably 0 to 5, is more preferably 0 to 1, is also preferably 0;
" g " represents 0 to 10, and is preferably 0 to 1, is more preferably 0;
" b+d+f " represents 0.01 to 100, and is preferably 0.1 to 10, is more preferably 0.5 to 2;
" a+b+c+d+e+f+g " represents 30 to 2700, and is preferably 60 to 1300, is more preferably 130 to 700;
R represents monovalent hydrocarbon independently of one another, has the alkoxy base of 1 to 5 carbon atom or oh group; And X represents the group being selected from amino group and epoxide group.
As for monovalent hydrocarbon, the example of monovalent hydrocarbon comprises the alkyl group with 1 to 30 carbon atom, the aromatic yl group with 6 to 30 carbon atoms, has the alkenyl group of 2 to 30 carbon atoms and have the aromatic alkyl group of 7 to 30 carbon atoms.The example of alkyl group, aromatic yl group, alkenyl group and aromatic alkyl group comprises the straight or branched alkyl group with 1 to 30 carbon atom, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl groups, heptyl groups and octyl groups; There is the group of naphthene base of 3 to 30 carbon atoms, such as cyclopentyl group and cyclohexyl groups; There is the aromatic yl group of 6 to 30 carbon atoms, such as phenyl group, tolyl group and xylyl group; There is the alkenyl group of 2 to 30 carbon atoms, such as vinyl groups, allyl group, butenyl group, hexenyl group and octenyl group; There is the aromatic alkyl group of 7 to 30 carbon atoms, such as benzyl group; And the hydrogen atom being wherein bonded to carbon atom is at least in part by those alkyl that the halogen atom of such as fluorine replaces.Preferably, alkyl group, aromatic yl group, alkenyl group and aromatic alkyl group are unsubstituted and have the alkyl group of 1 to 10 carbon atom, aromatic yl group, alkenyl group and aromatic alkyl group.Unsubstituted and there is the alkyl group of 1 to 6 carbon atom or aromatic yl group is preferred.Methyl group, ethyl group, propyl group or phenyl group are especially preferred.
As alkoxy base, methoxy group, ethoxy group, propoxy group etc. can be used.
Amino group is preferably the group be expressed from the next :-R
1-(NR
2cH
2cH
2)
l-NR
3r
4{ wherein R
1represent bivalent hydrocarbon radical; R
2, R
3and R
4the group representing hydrogen atom, monovalent hydrocarbon, carboxyl groups independently of one another or be expressed from the next :-CH
2cH (OH) R
5(wherein R
5represent hydrogen atom, monovalent hydrocarbon or carboxyl groups); R
2, R
3and R
4in at least one be hydrogen atom; And l is the integer of 0 to 5 }.As for monovalent hydrocarbon, can use above-mentioned those.
The example of bivalent hydrocarbon radical comprises the straight or branched and substituted or unsubstituted bivalent hydrocarbon radical with 1 to 30 carbon atom.The example of the straight or branched and substituted or unsubstituted bivalent hydrocarbon radical with 1 to 30 carbon atom comprises the straight or branched alkylidene group with 1 to 30 carbon atom, such as methylene group, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and eight methylene groups; There is the alkenylene group of 2 to 30 carbon atoms, such as ethenylene groups, allylidene group, butenylidene group, sub-hexenyl group and sub-octenyl group; There is the arylene group of 6 to 30 carbon atoms, such as phenylene group and diphenylene group; There is the alkylenearylene group of 7 to 30 carbon atoms, such as dimethylene phenylene group; And the hydrogen atom being wherein bonded to carbon atom is those alkyl of the halogen atom of such as fluorine at least in part.Bivalent hydrocarbon radical be preferably there is 1 to 30 carbon atom divalence, do not replace and saturated alkyl, and be preferably the straight or branched alkylidene group with 1 to 30 carbon atom.
As carboxyl groups, the carboxyl groups with 2 to 30 carbon atoms is preferred.Aliphatic acyl group is preferred.
Epoxide group is preferably selected from glycidoxyalkyl group group, epoxy cycloalkylalkyl group and oxiranylalkyl group group.
There is the method for the amino group of silicon bonding or the polysiloxane of epoxide group without concrete restriction for preparation of the present invention, but any method known in the art can be used.
Such as, there is the amino group of silicon bonding or the polysiloxane of epoxide group obtain by the hydrosilylation of following material:
I () has the polysiloxane of the hydrogen atom of organosilicon bonding, and
(ii) there is the organic compound of unsaturated aliphatic group.
The example of unsaturated aliphatic group comprises the aliphatic group with terminal unsaturation degree be expressed from the next: and-R '-C (R ")=CH
2(wherein R ' represents singly-bound or bivalent hydrocarbon radical; And R " represent hydrogen atom or monovalent hydrocarbon).Specifically, vinyl groups and allyl group are preferred.
Described organic compound comprises at least one amino group or epoxide group.
In order to carry out hydrosilylation rapidly at relatively low temperatures, preferably use catalyst.The example of operable catalyst comprises well known those as hydrosilylation catalysts, such as, and the such as compound of platinum, ruthenium, rhodium, palladium, osmium and iridium.Specifically, platinum compounds is available.The example of platinum compounds comprises chloroplatinic acid, platinum, carrier (such as aluminium oxide, silica or carbon black) support solid platinum, platinum-vinyl siloxane compound, platinum-phosphine compound, platinum-phosphite complexes and platinum alcoholate catalyst.For hydrosilylation, can by platinum with about 0.0001 % by weight to 0.1 % by weight amount use platinum catalyst.
For hydrosilylation, solvent can be used where necessary.The example of operable solvent comprises ether; Ketone, such as acetal and cyclohexanone; Ester; Phenol; Hydrocarbon; Halogenated hydrocarbons; And dimethyl polysiloxane.Hydrosilylation reactions can carry out about 10 minutes to 8 hours when using catalyst under about 20 DEG C to 150 DEG C and preferably about 40 DEG C to the temperature of 120 DEG C.
The polysiloxane with amino group or epoxide group can also be obtained by the equilibrium polymerization of following material:
(iii) cyclic polyorganosiloxane, and
(iv) there is the amino group of organosilicon bonding or the polysiloxane of epoxide group.
The example of cyclic polyorganosiloxane comprises hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, 1,3,5-trimethyl-1,3,5-triphenyl cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl cyclotetrasiloxane, hexaphenyl cyclotrisiloxane, octaphenylcyclotetrasiloxane, 1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetrasiloxane, six vinyl cyclotrisiloxane and eight vinyl cyclotetrasiloxanes.
For equilibrium polymerization, can balance polymerization catalyst.The example of equilibrium polymerization catalyst comprises alkali metal hydroxide, such as lithium hydroxide, NaOH, potassium hydroxide, cesium hydroxide, rubidium hydroxide, TMAH and tetrabutylphosphoniuhydroxide hydroxide phosphorus; Alkali metal silicon alkoxide, such as silanol lithium, sodium silanolate, silanol potassium, silanol caesium, tetramethyl silanol ammonium and tetrabutyl silanol phosphorus; And organo-metallic compound, such as butyl lithium, lithium methide, sodium naphthalene and potassium naphthalide.
In order to promote balanced reaction, the solvent promoting polymerization well-known in the art can be used.When using the solvent promoting polymerization, equilibrium polymerization is easy to carry out at relatively low temperatures, and can control the dissociation reaction of amide group in equilibrium polymerization process, and is therefore desirable.Promote that the example of the solvent of polymerization comprises polar organic solvent, such as oxolane, dimethyl formamide, dimethyl sulfoxide (DMSO) and acetonitrile.
As for the temperature of equilibrium polymerization, reaction is preferably made to carry out in the temperature range of 50 to 200 DEG C.Reaction is more preferably made to carry out in the temperature range of 50 to 150 DEG C.Especially reaction is preferably made to carry out in the temperature range of 50 to 140 DEG C.Equilibrium polymerization can carry out 10 minutes to 10 hours.
The polysiloxane of the amino group or epoxide group with silicon bonding can also be obtained by the condensation of following material: at strand two ends all by the diorganopolysiloxanecompositions of oh group end-blocking, and there is the alkoxy silane of functional group of silicon bonding, the alkoxy silane such as containing amino group or the alkoxy silane containing epoxide group.For condensation, condensation catalyst can be used.But, not need especially to use condensation catalyst.By make the alkoxy silane of the functional group with silicon bonding with lower than 2 moles, preferably 1.5 mole or less and more preferably 1 mole or less amount and 1 mole all reacted when not using catalyst by the diorganopolysiloxanecompositions of oh group end-blocking at strand two ends, the polysiloxane in one end of strand with the functional group of silicon bonding can be obtained.
Such as, obtain by the condensation of following material containing the polysiloxane as the amino group of the functional group of silicon bonding:
(v) be expressed from the next at strand two ends all by the diorganopolysiloxanecompositions of oh group end-blocking: HO-(SiR
6 2o)
x-H (wherein R
6represent monovalent hydrocarbon; And x is the number of 5 to 2700), and
(vi) organoalkoxysilane of amido-containing group expressed by the following formula: R
7 nr
8si (OR
9)
3-n(wherein R
7represent monovalent hydrocarbon; R
8represent following formula :-R
10-(NR
11cH
2cH
2)
m-NH-R
12(wherein R
10represent bivalent hydrocarbon radical; R
11and R
12represent hydrogen atom or monovalent hydrocarbon independently of one another; And m is the integer of 0 to 5); R
9represent monovalent hydrocarbon; And n is 0 or 1).As for monovalent hydrocarbon and bivalent hydrocarbon radical, can use above-mentioned those.
Condensation can be carried out under nitrogen atmosphere in the temperature range of 50 DEG C to 150 DEG C, maintains identical temperature simultaneously and removes the alcohol etc. produced as byproduct of reaction.Condensation can carry out about 10 minutes to 8 hours.
(C) polycarboxylic acids
Polycarboxylic acids is the crosslinking agent of Treatment Solution of the present invention.The example of acid or its salt can be: malic acid, oxo disuccinic acid, butanedioic acid, 1,2,3,4-BTCA, maleic acid, iminobisuccinate, sulfo-disuccinate, tricarballylic acid, citric acid, 1,2,3,4,5,6-cyclohexane hexacarboxylic acid, 1,2,3,4-cyclobutane tetrabasic carboxylic acid, propylene-1,2,3-tricarboxylic acids, 1,2,3,4-pentamethylene tetrabasic carboxylic acid, oxolane-2,3,4,5-tetrabasic carboxylic acid, 1,2,4-benzene tricarbonic acid, 1,2,4,5-benzene tertacarbonic acid and benzene hexacarboxylic acid.The preferred acid of beneficial effect can be provided to be oxo disuccinic acid, propylene-1,2,3-tricarboxylic acids and 1,2,3,4-BTCA.In addition, the sulfate containing the polymer of maleic acid and sulfate adduct may be there is in the product mixture.In a preferred embodiment, polycarboxylic acids is 1,2,3,4-BTCA (BTCA).
These polycarboxylic acids preferably add with the level of about 0.5% to about 75% of Treatment Solution of the present invention.
(D) esterification catalyst
The Treatment Solution of described fibrous cellulosic materials also includes and is beneficial to by the crosslinked esterification catalyst of the reactive site (cellulose in the fiber of the textiles of such as containing cellulose) on component (C) and textiles.Esterification catalyst of the present invention can be selected from multiple material, such as carbodiimide, carboxylic acid, mineral acid, lewis acid and phosphorus oxyacid.The catalyst that can adopt comprises cyanamide by way of example, guanidine or its salt, dicyandiamide, urea, dimethyl urea or thiocarbamide, the alkali metal salt of hypophosphorous acid, phosphorus or phosphorous acid, mineral acid, organic acid and salt thereof; More preferably inferior sodium phosphate, ortho phosphorous acid and sodium phosphate.
Preferred catalyst comprises cyanamide, cdicynanmide, urea, dimethyl urea, inferior sodium phosphate, phosphorous acid, sodium phosphate and composition thereof.Usually fabric is used a certain amount of catalyst treatment, this amount is enough to the crosslinked with the contraction providing durable press process and/or alleviate of catalysis natural fabric, and the I such as alleviated after washing shrinks.In one embodiment, can adopt catalyst by such amount, this amount is enough to provide about 0.05 to about 75 and the crosslinking agent of preferred about 1 to about 60: catalyst weight ratio.
(E) organic zirconate
Organic zirconate can be represented by organic zirconium ester or organic zirconium chelate.
This type of organic zirconium ester is well known in the art, and can be represented by four propyl alcohol zirconiums or four butanols zirconiums.
This type of organic zirconium chelate is well known in the art, and can be represented by following object lesson: zirconium (IV), hexafluoro zirconium acetylacetonate (IV), trifluoroacetyl group pyruvic acid zirconium (IV), four (ethyl trifluoroacetyl group pyruvic acid) zirconium, four (2, 2, 6, 6-tetramethyl-heptane thiosulfuric acid) zirconium, dibutoxy two (ethyl acetone acid) zirconium (IV), diisopropoxy two (2, 2, 6, 6-tetramethyl-heptane thiosulfuric acid) zirconium or have as part beta-diketon (comprise its alkyl replace with fluorine replace form) similar zirconium composite.
In these compounds most preferably acetoacetate zirconium composite (comprise alkyl replace with fluorine replace form).
(G) water (emulsion)
The Treatment Solution of fibrous cellulosic materials of the present invention uses by being dissolved in organic solvent.But in order to alleviate environmental pressure, Water-In-Oil or O/w emulsion form are preferred.In this case, water and emulsifying agent can be added the mixture of component (A) to (E) to make it emulsification.Water and emulsifying agent can be added each of component (A) and (B) to form preliminary emulsion, subsequently can by their mixing to prepare the Treatment Solution of the fibrous cellulosic materials of emulsion form.Emulsification method wherein used can be undertaken by conventional means or equipment.
(F) emulsifying agent
As the emulsifying agent of preparation above-mentioned emulsion, any emulsifying agent for the preparation of organic silicon emulsion can be used, and any emulsifying agent of such as anion, CATION, both sexes or nonionic emulsifier can be used.Emulsifying agent can use or combinationally using with its two or more type individually.
As the example of anion surfactant, such as saturated or unsaturated high-grade fatty acid salt, such as odium stearate etc. can be mentioned; Long chain alkyl sulfates, alkyl benzene sulphonate (such as DBSA etc.) and salt thereof; Polyoxyalkylene alkyl sulfate; Polyoxyalkylene alkenyl ether sulfate; Polyoxyethylene alkyl sulfate salt; Sulfosuccinic acid alkyl ester salt; Polyoxyalkylene thio succinate; Long chain alkane sulfonate; Polyoxyalkylene alkyl acetate; Chain alkyl phosphate; Polyoxyalkylene alkyl phosphate; Acyl glutamate; Alkanoylalkyl taurate; N-acyl amino hydrochlorate; Alkyl-alkyl ether carboxylate; Alpha-sulfo fatty acid ester salt; Alanine derivatives; Glycine derivative; Arginine derivative etc.As the example of aforementioned salt, alkali metal salt can be mentioned, such as sodium salt etc.; Alkanol amine salt etc., such as triethanolamine salt etc.; And ammonium salt.Sodium salt is preferred.
As the example of cationic surfactant, such as quaternary ammonium salt can be mentioned, such as alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt etc.
As the example of amphoteric surfactant, imidazoline type, amidobetaines alkaline, alkyl betaine-type, alkyl amido betaine type, alkyl sulfo betaines type, amidosulfobetaines type, hydroxy sulfo betaine type, carboxy betaine type, phosphate betaine type, aminocarboxylic acid type and amidoamino acid type amphoteric surfactant can be mentioned.
As the example of non-ionic surface active agent, such as polyoxyalkylene ether, polyoxyalkylene alkyl, polyoxyalkylene fatty acid ester, polyoxyalkylene fatty acid diester, polyoxyalkylene resins acid esters, polyoxyalkylene alkyl phenol, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ester, sorbitan aliphatic ester, polyoxyalkylene sorbitan aliphatic ester, polyoxyalkylene fatty acid glyceride, sucrose fatty ester, fatty acid alkanol amides, alkyl glucoside, polyoxyalkylene fatty acid diphenyl ether etc. can be mentioned.
other compositions
In non-curable coating composition of the present invention, can blended any additive within the scope without prejudice to the object of the present invention.As the example of aforementioned additive, such as viscosity modifier, pH adjusting agent, defoamer etc. can be mentioned.Type and the blending amount of additive suitably can be regulated according to the usage of non-curable coating composition of the present invention.
example:
The formula of preparation table 1 in the following manner: 1) each composition is added in the water of about 50 % by weight; 2) stir until evenly; 3) at room temperature emulsifying mixture is made; And 4) while stirring, interpolation water reaches final ratio.
Q2-8797: the functionalized organic silicon emulsion of amino group, the product of Dow Corning Corporation (Dow Corning Corp.), silicone content is about 30 % by weight.
Q2-8708: the functionalized organic silicon emulsion of epoxide group, the product of Dow Corning Corporation, silicone content is about 20 % by weight.
BTCA:1,2,3,4-BTCA
SHP: inferior sodium phosphate
Phobol XAN (PBN), the product of Huntsman Corporation (HUNTSMAN): the emulsion of the polyisocyanates of oxime protection, the content of the polyisocyanates of oxime protection is 40 % by weight.
The emulsion (CV-ZA EM) of tetra-acetylated pyruvic acid zirconium: the product of Dow Corning Corporation: the content of tetra-acetylated pyruvic acid zirconium is 15 % by weight.
COTTON FABRIC is made to pass through process bath, and saturated with process bath liquid composite.Process bath comprises the aqueous solution composition of table 1.Make saturated COTTON FABRIC by pressure roller, cause the wet Treatment Solution absorbing 50%-70% on fabric.Fabric is solidified 3 minutes at 160 DEG C in curing oven.
Measure the DP (grading of durable press outward appearance) of gained fabric according to AATCC method 124-2001, and measure the tearing strength of gained fabric according to ASTM method D1424-63.
table 1
Claims (11)
1. a Treatment Solution for fibrous cellulosic materials, it comprises:
(A) the functionalized organopolysiloxane of amino group,
(B) the functionalized organopolysiloxane of epoxide group,
(C) polycarboxylic acids,
(D) esterification catalyst,
(E) organic zirconate,
(F) emulsifying agent, and
(G) water.
2. Treatment Solution according to claim 1, it also comprises (H) copolymer-maleic anhydride or the isocyanates through protection.
3. Treatment Solution according to claim 1 and 2, it also comprises (I) polyalcohol.
4. Treatment Solution according to claim 1, the described organopolysiloxane of wherein said component (A) and (B) is the polysiloxane represented by following averaged unit formula:
((R)
3SiO
1/2)
a(XR
2SiO
1/2)
b(R
2SiO
2/2)
c(XRSiO
2/2)
d(RSiO
3/2)
e(XSiO
3/2)
f(SiO
4/2)
g
Wherein " a " represents the number of 0 to 50;
" b " represents the number of 0 to 50;
" c " represents the number of 30 to 2700;
" d " represents the number of 0 to 50;
" e " represents the number of 0 to 50;
" f " represents the number of 0 to 50;
" g " represents the number of 0 to 10;
" b+d+f " represents the number of 0.01 to 100;
" a+b+c+d+e+f+g " represents the number of 30 to 2700;
R represents monovalent hydrocarbon independently of one another, has the alkoxy base of 1 to 5 carbon atom or oh group; And
X represents the group being selected from amino group and epoxide group.
5. Treatment Solution according to claim 4, wherein said monovalent hydrocarbon comprises the alkyl group with 1 to 30 carbon atom, the aromatic yl group with 6 to 30 carbon atoms, has the alkenyl group of 2 to 30 carbon atoms and have the aromatic alkyl group of 7 to 30 carbon atoms.
6. Treatment Solution according to claim 4, wherein said amino group is the group be expressed from the next :-R
1-(NR
2cH
2cH
2)
l-NR
3r
4, wherein R
1represent the bivalent hydrocarbon radical with 1 to 30 carbon atom; R
2, R
3and R
4the group representing hydrogen atom, monovalent hydrocarbon, carboxyl groups independently of one another or be expressed from the next :-CH
2cH (OH) R
5, wherein R
5represent hydrogen atom, monovalent hydrocarbon or carboxyl groups; R
2, R
3and R
4in at least one be hydrogen atom; And l is the integer of 0 to 5.
7. Treatment Solution according to claim 4, wherein said epoxide group is selected from glycidoxyalkyl group group, epoxy cycloalkylalkyl group and oxiranylalkyl group group.
8. Treatment Solution according to claim 1, wherein said polycarboxylic acids is selected from: malic acid, oxo disuccinic acid, butanedioic acid, 1,2,3,4-BTCA, maleic acid, tricarballylic acid, citric acid, 1,2,3,4,5,6-cyclohexane hexacarboxylic acid, 1,2,3,4-cyclobutane tetrabasic carboxylic acid, propylene-1,2,3-tricarboxylic acids, 1,2,3,4-pentamethylene tetrabasic carboxylic acid, oxolane-2,3,4,5-tetrabasic carboxylic acid, 1,2,4-benzene tricarbonic acid, 1,2,4,5-benzene tertacarbonic acid and benzene hexacarboxylic acid.
9. Treatment Solution according to claim 1, wherein said esterification catalyst is selected from: carbodiimide, carboxylic acid, mineral acid, lewis acid and phosphorus oxyacid.
10. Treatment Solution according to claim 1, wherein said organic zirconate is selected from: four propyl alcohol zirconiums and four butanols zirconiums.
11. Treatment Solution according to claim 1, wherein said emulsifying agent is selected from: anion emulsifier, cationic emulsifier, amphoteric emulsifier and nonionic emulsifier.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2012/082148 WO2014047833A1 (en) | 2012-09-27 | 2012-09-27 | Treating solution for fibrous cellulosic material |
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| Publication Number | Publication Date |
|---|---|
| CN104350199A true CN104350199A (en) | 2015-02-11 |
Family
ID=50386814
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|---|---|---|---|
| CN201280073886.1A Pending CN104350199A (en) | 2012-09-27 | 2012-09-27 | Treating solution for fibrous cellulosic material |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2900862A1 (en) |
| JP (1) | JP2015526569A (en) |
| CN (1) | CN104350199A (en) |
| WO (1) | WO2014047833A1 (en) |
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|---|---|---|---|---|
| JP6454047B1 (en) * | 2018-06-28 | 2019-01-16 | 竹本油脂株式会社 | Viscose rayon nonwoven treatment agent and viscose rayon |
| US10982050B2 (en) * | 2019-04-25 | 2021-04-20 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Sealing composite material, preparation method, and application thereof |
| WO2023118811A1 (en) * | 2021-12-22 | 2023-06-29 | Uea Enterprises Limited | A method of modifying cellulose fibres and/or cellulose fabric |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0058493A1 (en) * | 1981-02-05 | 1982-08-25 | Toray Silicone Company Limited | Fiber-treating compositions comprising two organo-functional polysiloxanes |
| US4399247A (en) * | 1981-06-26 | 1983-08-16 | Toray Silicone Company, Ltd. | Organopolysiloxane-containing composition for treating substrates |
| CN87103755A (en) * | 1986-05-22 | 1987-12-09 | 信越化学工业株式会社 | Siloxane-based synthetic fiber finishing agent |
| CN101638847A (en) * | 2009-07-24 | 2010-02-03 | 东莞市德能化工有限公司 | Formaldehyde-free durable crease-proof finishing agent used for cellulosic fiber fabric |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0207744D0 (en) * | 2002-04-03 | 2002-05-15 | Unilever Plc | Fabric care composition |
-
2012
- 2012-09-27 JP JP2015528831A patent/JP2015526569A/en active Pending
- 2012-09-27 EP EP12885501.2A patent/EP2900862A1/en not_active Withdrawn
- 2012-09-27 WO PCT/CN2012/082148 patent/WO2014047833A1/en active Application Filing
- 2012-09-27 CN CN201280073886.1A patent/CN104350199A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0058493A1 (en) * | 1981-02-05 | 1982-08-25 | Toray Silicone Company Limited | Fiber-treating compositions comprising two organo-functional polysiloxanes |
| US4399247A (en) * | 1981-06-26 | 1983-08-16 | Toray Silicone Company, Ltd. | Organopolysiloxane-containing composition for treating substrates |
| CN87103755A (en) * | 1986-05-22 | 1987-12-09 | 信越化学工业株式会社 | Siloxane-based synthetic fiber finishing agent |
| CN101638847A (en) * | 2009-07-24 | 2010-02-03 | 东莞市德能化工有限公司 | Formaldehyde-free durable crease-proof finishing agent used for cellulosic fiber fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014047833A1 (en) | 2014-04-03 |
| JP2015526569A (en) | 2015-09-10 |
| EP2900862A1 (en) | 2015-08-05 |
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