CN105332278B - The environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth - Google Patents
The environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth Download PDFInfo
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- CN105332278B CN105332278B CN201510837315.6A CN201510837315A CN105332278B CN 105332278 B CN105332278 B CN 105332278B CN 201510837315 A CN201510837315 A CN 201510837315A CN 105332278 B CN105332278 B CN 105332278B
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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
- D06M13/322—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 nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
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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
- D06M13/244—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 sulfur or phosphorus
- D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
- D06M13/295—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing polyglycol moieties; containing neopentyl moieties
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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
- D06M15/53—Polyethers
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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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
Abstract
The present invention relates to a kind of environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth, it is characterised in that the hydrophilizing agent, contains：(A) 25~45% phosphate type the moon/nonionic wetting and penetrating agent；(B) 10~30% Shuangzi nonionic surfactant；(C) 15~25% hydroxyl phosphate beet alkali ampholytic surface active agent；(D) 20~40% macromolecule nonionic surfactant.The present invention is using vegetable oil derivatives as hydrophobic group primary raw material, and preparation process is relatively simple, atom utilization is high, without poisonous and harmful intermediate, and adverse effect is small to caused by environment；In use to skin without irritating；Under field conditions (factors) compared with easily biological-degradable after discarded, cause new pollution small to environment, be a kind of environmentally friendly hydrophilizing agent；Due to the cooperative effect of anion, both sexes, Shuangzi and high molecular type surfactant, the polyolefm non-woven cloth that can make to be organized has preferably instantaneous, more excellent multiple water penetration.
Description
Technical field
The present invention relates to the auxiliary agent used in being processed in disposable sanitary articles, and in particular to a kind of environmentally friendly polyene
The multiple hydrophilic finishing agent of hydrocarbon non-woven cloth.
Background technology
The quality of life and social development band of the mankind is given in disposable medical, health care, the invention of amenities and extensive use
Carry out huge benefit, also bring brand-new life style.Absorbability disposable sanitary articles, including feminine hygiene
The amenities such as articles for use, diaper for babies, adult-incontinence articles, wet tissue, pet pads, in recent years the market scale in China persistently increase
Long, by 62,100,000,000 yuan of 40,000,000,000 yuan to 2013 of 2010, average annual growth rate is more than 13%.
Currently used polyolefm non-woven cloth includes polypropylene and polyethylene/polypropylene composite-fiber nonwoven fabric, by
It is used widely in its excellent performance and cheap price in medicine and hygiene fieldses, clothes cloth, Wiping material etc..
Because the fiber is non-polar conformations, crystallinity is high and molecule in without hydrophilic group, while fibre section is rounded, compact structure
Lack micropore and gap, the non-woven cloth that thus material is formed without moisture absorption, absorbent function, limits answering in above-mentioned field substantially
With so hydrophilic modifying must be carried out to it.
The hydrophilic modification method of polyolefine fiber has two kinds：Physics and chemical modification.Chemical modification mainly changes polyene
The molecular chain structure of hydrocarbon, and then change its hygroscopicity, mainly there is the methods of copolymerization, grafting, crosslinking, plasma surface treatment；
Physical modification mainly has blending and modifying and surface hydrophilic to arrange and be modified.
Chemistry and blending and modifying can keep the persistence of hydrophilic effect, but process is complicated, cost is high, and to the suction of fiber
Wet, water absorption raising is limited, it is difficult to which " the instantaneous water suction " for reaching disposable sanitary articles requires.Final finishing is hydrophilic by contrast
Modification has the characteristics that method simplicity, significant effect, cost are cheap, can increase in the case where keeping fiber primary characteristic substantially
Adding the hygroscopicity and water imbibition, improvement comfortableness of fiber, shortcoming is that durability is relatively poor, but due to disposable non-woven cloth pair
Life requirement is not high, has turned into and has applied a kind of method the most universal.
The hydrophilic finishing agent used in polyolefm non-woven cloth is mostly that different types of water soluble surfactant active answers at present
With thing, because short-chain branch type sulfonic acid or Sulfates have preferably infiltration compared with carboxylic acid or phosphoric acid salt anion surfactant
And hydrophily, so, wherein more main components using sulfosuccinate diisooctyl sulfosuccinate as wetting and fast permeable speed effect,
Compound auxiliary is mostly low molecular the moon/nonionic, nonionic surfactant or adds high molecular surfactant.The former is such as：
Isomery alkyl alcohol ether sodium sulfonate, etherificate potassium alkyl phosphate, high-carbon fatty alcohol polyoxyethylene ether etc.；The latter：Polyether-modified silicon
Oily, lauryl alcohol polyoxyethylene (15) ether maleic mono-ester/acrylic copolymer sodium salt etc..Mainly considered in formula designs
Hydrophilic validity, the low excitatory and comfortableness used, but not using raw materials used environment friendly as considering emphasis,
The silicone backbone and the high polymer of carbon-carbon backbone chain that the latter is contained in being particularly formulated, though only low toxicity or non-toxic,
It is difficult to biodegradation.
Disposable " disposable " product, the amount quickly by number in terms of ten thousand tons is switched to discard after flow into the market places
Thing, finally nature is discharged into including its hydrophilic additive including surface attachment, soil, water and atmospheric environment are produced dirty
Dye.So as the hydrophilic finishing agent used in disposable hygienic material surface, be also necessary to consider raw material, manufacturing process and
The greenization of product, i.e., to use natural or regenerated resources, as raw material, process is pollution-free；Final products are nontoxic to human body,
Excitant is small and is readily biodegradable the design object as hydrophilizing agent.
The content of the invention
The technical problem to be solved in the present invention is：Based on above mentioned problem, the present invention provides a kind of environmentally friendly polyolefin
The multiple hydrophilic finishing agent of non-woven cloth, it takes into account hydrophilic validity, the satisfaction property of hydrophilic finiss technique and raw material, processed
Journey, the green of product.
The technical solution adopted for the present invention to solve the technical problems is：A kind of environmentally friendly polyolefm non-woven is provided
The multiple hydrophilic finishing agent of cloth, contains：
(A) 25~45% phosphate type the moon/nonionic wetting and penetrating agent, the wherein the moon/nonionic wetting and penetrating agent have
Phosplate the moon/nonionic wetting and penetrating agent of formula (I) and biphosphonate the moon/nonionic wetting and penetrating agent of formula (II),
And both mol ratios are 1：0.8~1.0,
Wherein, R is iso-octyl or isomery tridecyl, and n is 3~5, M+For ammonium, amine or sodium ion；
(B) 10~30% Shuangzi nonionic surfactant, the Shuangzi nonionic surfactant are that vegetable oil acid is polynary
Alcohol dibasic acid esters APEO, vegetable oil acid include the C from vegetable oil12~C18Saturation or unrighted acid；Polyalcohol includes
3~6 yuan of multi-alcohols such as glycerine, two polyglycereol, trimethylolpropane, pentaerythrite, sorbierite；Ring in per molecular
The total addition molal quantity of oxidative ethane is 18~40；
(C) 15~25% hydroxyl phosphate beet alkali ampholytic surface active agent, the surfactant are aliphatic acid epoxy-type hydroxyl
Base phosphate glycine betaine, it is 3-(N-(2-alkanoyloxy ethyl)-N, N-Dimethyl Ammonium)-2-hydroxyls of formula (III)
The 3 of base propyl group acid phosphoric acid ester glycine betaine or formula (IV)-(N-(3-alkanoyloxy-2-hydroxypropyl)-N, N-bis-
Ammonium methyl) one kind in-2-hydroxypropyl acid phosphoric acid ester glycine betaine,
Wherein：R2For the C from vegetable oil12~C18Saturation or unrighted acid, M1 +For sodium ion；
(D) 20~40% macromolecule nonionic surfactant, it is condensed for dimeric dibasic acid/APEO of formula (V)
One kind in the dimeric dibasic acid/oleic acid or stearic acid monoglycerides APEO condensation product of thing or formula (VI),
HO(CH2CH2O)m1(R3O(CH2CH2O)m1)n1H (Ⅴ)
Wherein：R3For dimeric dibasic acid acyl group；R4For stearic acid acyl group or oleic acid acyl group.m1For 18~36, n1For 5~10；m2For
13~26, n2For 3~7.
Isomery alkyl polyoxyethylene ether phosphate ammonium, amine or sodium salt selected by component (A), it is different pungent with sulfosuccinate two
Ester sodium salt is compared, and phosphate is excitatory with lower skin, and because inserting non-ionic polyoxyethylene ether in hydrophilic group
Group, make excitatory further reduction, the increase of nonwoven fabric nonwatertight speed.The two is respectively provided with relatively low surface tension and close, but
Only two kinds of surfactants of one pack system are compared, sulfonate is better than phosphate in permeable speed, and this is also at present hydrophilic
In agent prescription mostly phosphate free class surfactant the main reason for；The manufacturing process effect on environment of component (A) is small, atom
Utilization rate is high.The product neutralizes, entirely using long chain isomerism alcohol as initiator with ethyleneoxide addition, phosphorus pentoxide phosphorylation, alkali
Portion's process three wastes produce, by whole atoms that raw material introduces except final step has water generation to stay in product China and foreign countries, remaining whole
It is converted into product, atom conversion ratio is close to 100%.
M in component (A)+For ammonium, amine or sodium ion.To the excitatory of skin, the ammonium salt ≈ amine salt ＜ sodium salts of phosphate
＜ sylvite.The increase of nonwoven fabric nonwatertight speed order with it is upper opposite：Ammonium salt ≈ amine salt ＞ sodium salt ＞ sylvite.
Component (B) using renewable resources such as vegetable oil acid, glycerine, two polyglycereol, sorbierites as raw material, through vegetable oil acid with
Double esterification, the addition of ethylene oxide of multi-alcohol, double type nonionic surfactant is formed, removes and is being esterified in manufacturing process
Stage has water to be discharged into outside environment, and remaining is converted into product entirely, is Green Chemistry.The product formed is hydrophilic group mean molecule quantity
800~1700, the non-ionic (polymeric surfactant) (molecular weight 10 of average total molecular weight 1400~25003~106), category
In less toxic, low excitatory material.It is chemically reactive and biodegradable due to its esters nonionic.
Shuangzi Surfactant fundamentally overcomes traditional isolated subtype surfactant due to the electricity between ion head base
Separation tendency caused by lotus repulsion or aquation, promotes its close-packed arrays in interface or molecule aggregate, adsorption and
Reduce the increase of surface tension ability.Because high nonwoven fabric nonwatertight speed is dependent on the low surface tension of surfactant and high suction
It is water-based to realize, so component (B) and component (A's) is used in mixed way, mixing and absorption is formed in hydrophobic surface, alleviates surface
Tension force is low with the small contradiction of hydrophily；Again due to component (B) non-ionic hydrophilic, the oxygen atom of long chain ethoxylates is in water
In due to adsorbable part hydrogen ion and micro- electropositive, or non-ionic hydrophilic have polarity, the positive and negative charge center of molecule
It is separable, interacted, made on polyolefine fiber by the ionic group of dipole moment and component (A) anion surfactant
Mixed surfactant adsorption layer arranges closer, increases aqueous transmission capacity, and reduction is organized the nonwoven fabric nonwatertight time.
Component (C) is 3-(N-(2-alkanoyloxy ethyl)-N, N-Dimethyl Ammonium)-2-hydroxypropyl acid phosphorus
Acid esters glycine betaine, it is using vegetable oil acid, dimethylethanolamine, epoxychloropropane, sodium dihydrogen phosphate as primary raw material, or component
(C) it is 3-(N-(3-alkanoyloxy-2-hydroxypropyl)-N, N-Dimethyl Ammonium)-2-hydroxypropyl acid phosphoric acid esters
Glycine betaine, using vegetable oil acid, epoxychloropropane, 33% dimethylamine agueous solution, sodium dihydrogen phosphate as primary raw material, three steps of reaction point
Carry out, all processes are completed under the conditions of normal pressure or low pressure (＜ 0.1MPa), less than 85 DEG C.Raw material is cheap, be easy to get, toxicity compared with
It is low, special installation is not required to, reaction condition is gentle, easy controlled operation, and yield is higher.Byproduct sodium chloride (filtering filter in production process
Except), more disposable, effect on environment is small.Needed using ethanol as solvent in actual production and after the completion of reacting in different steps
Steam excessive add and do not participate in the epoxychloropropane or dimethylamine of reaction, but can reuse, effect on environment can be reduced.
Component (C) is aliphatic acid epoxy-type hydroxyl phosphate glycine betaine, and biology is more easy to compared with alkyl betaine or sulfobetaines
Degrade, to skin milder, can effectively reduce the anion surfactant excitant being used in mixed way.On hydrophilicity with the moon
Ion a and the combination of nonionic b components, produce more preferably permeation rate cooperative effect, and increase the soft comfortable of non-woven cloth.
The content range of the moon of instant component (A)/nonionic wetting and penetrating agent is 30~40%.
The content range of the Shuangzi nonionic surfactant of instant component (B) is 15~25%.
The content range of the hydroxyl phosphate beet alkali ampholytic surface active agent of instant component (C) is 10~20%.
The content range of the macromolecule nonionic surfactant of instant component (D) is 25~35%.
The macromolecule nonionic surfactant of instant component (D) is dimeric dibasic acid/APEO condensation polymer, and it is prepared
Method is as follows：
A, ethyleneoxide addition polymerization prepares polyoxyethylene ether dimeric acid esters：Dimeric dibasic acid 565kg is added into reactor,
Potassium hydroxide 2.0kg, open and be heated with stirring to 150~170 DEG C, be evacuated to -0.08~-0.09MPa, be dehydrated 20 minutes, close
Vacuum valve, inflated with nitrogen is to 0.06MPa, then is evacuated to -0.08MPa, inflated with nitrogen, common 3 times repeatedly, denitrogen gas to pressure-fired, begins
After adding oxirane, question response steady, 150 ± 5 DEG C of controlling reaction temperature, 0.2~0.3MPa of pressure, co-continuous addition epoxy second
1500~3000kg of alkane, treat all to add, after kettle pressure drop to about 0 gauge pressure, holding continues reaction 20 minutes, taken out very under this condition
It is empty 15 minutes, less than 70 DEG C are cooled to, acetic acid on the rocks adjusts pH to 6~7, discharging.
B, condensation polymerization prepares dimeric dibasic acid/APEO condensation polymer：Dimeric dibasic acid 100kg, step are added into reactor
(a) product polyoxyethylene ether dimeric 430~940kg of acid esters, the two mol ratio 1：1.2~1.5, composite catalyst 0.5~
1.0kg, 120 DEG C are heated with stirring to, are evacuated to gauge pressure≤- 0.09MPa, 160~180 DEG C of maintenance reaction temperature is extremely substantially anhydrous
Abjection, continue to be dehydrated half an hour, be cooled to 70 DEG C with bottom discharge, obtain dimeric dibasic acid/APEO condensation polymer.
The macromolecule nonionic surfactant of instant component (D) is dimeric dibasic acid/oleic acid or stearic acid monoglycerides polyoxy
Vinethene condensation polymer, its preparation method are as follows：
A, ethyleneoxide addition polymerization prepares oleic acid or stearic acid monoglycerides APEO：Oil is added into reactor
Acid or stearic acid monoglycerides 1kmol, potassium hydroxide 0.6kg, open and are heated with stirring to 130~150 DEG C, it is evacuated to -0.08~-
0.09MPa, it is dehydrated 20 minutes, closes vacuum valve, inflated with nitrogen is to 0.06MPa, then is evacuated to -0.08MPa, inflated with nitrogen, anti-altogether
It is multiple 3 times, denitrogen gas to pressure-fired, begin to add oxirane, after question response is steady, 140 ± 5 DEG C of controlling reaction temperature, pressure 0.2~
0.3MPa, co-continuous addition 26~52kmol of oxirane, treat all to add, after kettle pressure drop to nearly 0 gauge pressure, be maintained at the condition
Under continue reaction 20 minutes, vacuumize 15 minutes, be cooled to less than 70 DEG C, acetic acid on the rocks adjusts pH to 6~7, discharges.
B, condensation polymerization prepares dimeric dibasic acid/oleic acid or stearic acid monoglycerides APEO condensation polymer：Add into reactor
Enter dimeric dibasic acid 1kmol, the product oleic acid of step (a) or stearic acid monoglycerides APEO 1.35~1.15kmol, it is compound to urge
Agent 0.3~0.6%, about 120 DEG C are heated with stirring to, are evacuated to gauge pressure≤- 0.09MPa, maintenance reaction temperature 160~180
DEG C to substantially anhydrous abjection, continue to be dehydrated half an hour, be cooled to 70 DEG C with bottom discharge, obtain dimeric dibasic acid/oleic acid or stearic acid list
Sweet ester APEO condensation polymer.
Dimeric dibasic acid is C 18 unsaturated fatty acid dimer, is dryness, semi-drying such as soybean oil, cotton seed oil, rice bran oil
Deng the derivative of vegetable oil；The carboxylate of the oleic acid of oleic acid or stearic acid monoglycerides from vegetable oil, stearic acid and glycerine etc..Group
Divide the dimeric dibasic acid/APEO condensation polymer or dimeric dibasic acid/oleic acid or stearic acid monoglycerides APEO condensation polymer difference of (D)
Using dimeric dibasic acid, oleic acid or stearic acid monoglycerides as initiator, product is obtained with ethyleneoxide addition, esterification, preparation technology is simple,
Atom utilization is high.It is equivalent to the mean molecule quantity for being connected with APEO hydrophilic group on each dimerization acid molecule in product
790~1600, the average total molecular weight 8000~16000 of product, belong to non-ionic (polymeric surfactant), have to life
Thing it is micro- poison and to skin without excitatory.Because connecting APEO macromolecular main chain with ester bond, with mentioning in technical background
Organosilicon is different with carbon-carbon alkane hydrophobic backbone, has good hydrophily, chemically reactive and biodegradable.
Component (D) is formed by being connected with several hydrophobic side chains on hydrophilic macromolecular main chain, and each side chain is C17
Or C34Alkane, there is characteristic of the high molecular surfactant in hydrophobic surface strong adsorption force, with foregoing component (A), component (B)
Mixed micelle can be formed in aqueous phase after being compounded with component (C), the list of hydrophilic group outside (insertion aqueous phase) is formed in fiber surface
(or more) molecular layer adsorption film.Due to the effect of high molecular surfactant, low-molecular-weight surfactant is limited to through-fall
In diffusion velocity and the migration velocity along fiber surface, add hydrophilic muptiple-use.
Component (D) polymerization degree n1For 5~10, n2For 3~7, such as it is less than lower limit, hydrophilic muptiple-use increase unobvious；Higher than upper
Limit, it is bad with first three component compatibility, influence the transparency of hydrophilizing agent stoste.Ethyleneoxide addition molal quantity m1For 18~36, m2
It is too high higher than upper limit hydrophily less than floor effects hydrophilizing agent permeation rate for 13~26, under the absorption affinity of hydrophobic surface
Drop, hydrophilic permeability time is caused repeatedly to gather way increase.
The beneficial effects of the invention are as follows：Selected each component in hydrophilizing agent of the present invention, in addition to component (A), other each groups
The hydrophobic group and the raw material of part hydrophilic group divided belongs to renewable resource both from vegetable oil；Preparation process is simple, atom is sharp
Produced with rate height, without poisonous and harmful substance, adverse effect is small to caused by environment；In use to skin without irritating；It is useless
Cause new pollution small to environment compared with easily biological-degradable under field conditions (factors) after abandoning, be a kind of environmentally friendly hydrophilizing agent；
2. from phosphate type the moon/nonionic wetting and penetrating agent of component (A), with macromolecule Shuangzi non-ionic surface active
Agent, aliphatic acid epoxy-type hydroxyl phosphate beet alkali ampholytic surface active agent are hydrophilic synergist；Gathered with the hydrophily that ester bond connects
Oxygen vinethene is that the oligomeric-type high molecular surfactant of main chain is multiple hydrophilic potentiating agent, makes processed polyolefm non-woven
Cloth have with the hydrophilizing agent containing sulfonic acid or Sulfates surfactant similar in instantaneous, more excellent multiple water penetration, preferably
Skin mildness.
Embodiment
Presently in connection with specific embodiment, the invention will be further described, following examples be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1
1.1st, it is formulated：
Component (A)：Iso-octyl APEO (3) phosphoric acid ester ammonium salt (single dibasic acid esters mol ratio about 1：1)：28%,
Component (B)：Two polyglycereol laurate dibasic acid esters APEO (20) esters：16%,
Component (C)：3-{ N-(2-bay trimethylammonium)-N, N-Dimethyl Ammonium }-2-hydroxypropyl acid phosphorus
Acid esters sodium glycine betaine：12%,
Component (D)：Dimeric dibasic acid/oleic acid monoglyceride APEO (40) condensation polymer (m2≈ 20, condensation degree n2≈5)：
24%,
Separately add water：20%；
1.2nd, the preparation of component (D)：
A, ethyleneoxide addition polymerization prepares oleic acid monoglyceride APEO：Oleic acid monoglyceride is added into reactor
354kg, potassium hydroxide 0.7kg, open and be heated with stirring to 130~150 DEG C, be evacuated to -0.08~-0.09MPa, be dehydrated 20 points
Clock, vacuum valve is closed, inflated with nitrogen is to 0.06MPa, then is evacuated to -0.08MPa, inflated with nitrogen, repeatedly 3 times altogether, and denitrogen gas is to micro-
Malleation, begins plus oxirane, after question response is steady, 140 ± 5 DEG C of controlling reaction temperature, pressure 0.2~0.3MPa, it is co-continuous plus
Enter oxirane 1760kg, treat all to add, after kettle pressure drop to about 0 gauge pressure, holding continues reaction 20 minutes, taken out under this condition
Vacuum 15 minutes, less than 70 DEG C are cooled to, acetic acid on the rocks adjusts pH to 6~7, discharging；
2., condensation polymerization：Dimeric dibasic acid 113kg, the oleic acid monoglyceride APEO of step (a) are added into reactor
500kg, composite catalyst 0.6kg, about 120 DEG C are heated with stirring to, are evacuated to gauge pressure≤- 0.09MPa, maintenance reaction temperature
160~180 DEG C, to substantially anhydrous abjection, are continued to be dehydrated half an hour, are cooled to 70 DEG C with bottom discharge, obtain dimeric dibasic acid/oleic acid list
Sweet ester APEO condensation polymer.
1.3rd, hydrophilic finishing agent is allocated：
Into reactor add formula in water, sequentially add formula in component (A), component (B), component (C) and
Component (D), to open stirring and be warming up to 60 DEG C, continue stirring 10 minutes, kettle liquid is in light yellow transparent liquid, cools to less than 50 DEG C,
Discharging, filtering, packaging.
Embodiment 2
2.1st, it is formulated：
Component (A)：Isomery Sodium Trideceth (5) phosphoric acid ester ammonium salt (single dibasic acid esters mol ratio about 1：1)：28%,
Component (B)：Two polyglycereol Glycol Oleic Acid Ester APEO (30) esters：16%,
Component (C)：3-{ N-(3-oleoyl epoxide-2-hydroxypropyl)-N, N-Dimethyl Ammonium }-2-hydroxyls third
Base acid phosphoric acid ester sodium glycine betaine：12%,
Component (D)：Dimeric dibasic acid/APEO (25) condensation polymer (m1≈ 25, condensation degree n1≈9)：24%,
Separately add water：20%；
2.2nd, the preparation of component (D)：
A, ethyleneoxide addition polymerization prepares polyoxyethylene ether dimeric acid esters：Dimeric dibasic acid 565kg is added into reactor,
Potassium hydroxide 2.0kg, open and be heated with stirring to 150~170 DEG C, be evacuated to -0.08~-0.09MPa, be dehydrated 20 minutes, close
Vacuum valve, inflated with nitrogen is to 0.06MPa, then is evacuated to -0.08MPa, inflated with nitrogen, common 3 times repeatedly, denitrogen gas to pressure-fired, begins
After adding oxirane, question response steady, 150 ± 5 DEG C of controlling reaction temperature, 0.2~0.3MPa of pressure, co-continuous addition epoxy second
Alkane 2200kg, treat all to add, after kettle pressure drop to about 0 gauge pressure, holding continues reaction 20 minutes, vacuumizes 15 points under this condition
Clock, less than 70 DEG C are cooled to, acetic acid on the rocks adjusts pH to 6~7, discharging；
B, condensation polymerization：Dimeric dibasic acid 113kg, the polyoxyethylene ether dimeric acid esters of step (a) are added into reactor
690kg, composite catalyst 0.5kg, about 120 DEG C are heated with stirring to, are evacuated to gauge pressure≤- 0.09MPa, maintenance reaction temperature
160~180 DEG C, to substantially anhydrous abjection, are continued to be dehydrated half an hour, are cooled to 70 DEG C with bottom discharge, obtain dimeric dibasic acid/polyoxy second
Alkene ether condensation polymer.
2.3rd, hydrophilic finishing agent is allocated：
Into reactor add formula in water, sequentially add formula in component (A), component (B), component (C) and
Component (D), to open stirring and be warming up to 60 DEG C, continue stirring 10 minutes, kettle liquid is in light yellow transparent liquid, cools to less than 50 DEG C,
Discharging, filtering, packaging.
Application performance：
1st, skin harmfulness is tested：
Sample：16.5g/m polypropylene fibre SS Spunbonded Nonwovens, the hydrophilizing agent average content 0.66% of embodiment 1, testing result
It is as follows：
Skin is excitatory/corrosion test：It is 0 that tested material, which irritates reaction integrated value to family's rabbit skin, and it is nothing to irritate intensity
It is excitatory.
Skin allergy test：Tested material sensitization rate (%)=0, according to sensitization strength grading standard, the sample has no
Skin allergic reaction.
2nd, water penetration is tested
Detection method：With reference to the part of GB/T 24218.12-2012 textile non-woven cloths test method the 13rd：Liquid is more
The measure of secondary time of break-through.
Testing result is as shown in table 1 below：
Note：Standard specimen is the multiple hydrophilizing agent that Nonwovens Enterprises use online.
Embodiment sample：16.5g/m polypropylene fibre SS Spunbonded Nonwovens, hydrophilizing agent average content 0.66%,
The data from table 1, compared with standard specimen, the 1st, the 2nd simulation urine time of break-through, which is slightly above standard specimen, (can expire
Sufficient user's requirement), but the 3rd~5 time of break-through is less than standard specimen, and the fall off rate of time of break-through is gradually reduced, the 5th
Time of break-through reduces 14% and 17%.
It is complete by above-mentioned description, relevant staff using the above-mentioned desirable embodiment according to the present invention as enlightenment
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to determines its technical scope according to right.
Claims (7)
1. the environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth, it is characterised in that：Contain：
(A) 25~45% phosphate type the moon/nonionic wetting and penetrating agent, the wherein the moon/nonionic wetting and penetrating agent have formula
(I) phosplate the moon/nonionic wetting and penetrating agent and biphosphonate the moon/nonionic wetting and penetrating agent of formula (II), and two
The mol ratio of person is 1：0.8~1.0,
Wherein, R is iso-octyl or isomery tridecyl, and n is 3~5, M+For ammonium, amine or sodium ion；
(B) 10~30% Shuangzi nonionic surfactant, the Shuangzi nonionic surfactant are that vegetable oil acid polyalcohol is double
Ester APEO, vegetable oil acid include the C from vegetable oil12~C18Saturation or unrighted acid；Polyalcohol includes sweet
Oil, two polyglycereol, trimethylolpropane, pentaerythrite or sorbierite；The total addition molal quantity of oxirane in per molecular
For 18~40；
(C) 15~25% hydroxyl phosphate beet alkali ampholytic surface active agent, the surfactant are aliphatic acid epoxy-type hydroxyl phosphorus
Acid esters glycine betaine, it is 3-(N-(2-alkanoyloxy ethyl)-N, N-Dimethyl Ammonium)-2-hydroxyls third of formula (III)
3-(N-(3-alkanoyloxy-2-hydroxypropyl)-N, N-dimethyl of base acid phosphoric acid ester glycine betaine or formula (IV)
Ammonium) one kind in-2-hydroxypropyl acid phosphoric acid ester glycine betaine,
Wherein：R2For the C from vegetable oil12~C18Saturation or unrighted acid, M1 +For sodium ion；
(D) 20~40% macromolecule nonionic surfactant, its for formula (V) dimeric dibasic acid/APEO condensation polymer or
One kind in the dimeric dibasic acid/oleic acid or stearic acid monoglycerides APEO condensation polymer of formula (VI),
HO(CH2CH2O)m1(R3O(CH2CH2O)m1)n1H (Ⅴ)
Wherein：R3For dimeric dibasic acid acyl group；R4For stearic acid acyl group or oleic acid acyl group, m1For 18~36, n1For 5~10；m2For 13~
26, n2For 3~7.
2. the environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth according to claim 1, it is characterised in that：Group
The content range for dividing the moon/nonionic wetting and penetrating agent of (A) is 30~40%.
3. the environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth according to claim 1, it is characterised in that：Group
The content range for dividing the Shuangzi nonionic surfactant of (B) is 15~25%.
4. the environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth according to claim 1, it is characterised in that：Group
The content range for dividing the hydroxyl phosphate beet alkali ampholytic surface active agent of (C) is 10~20%.
5. the environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth according to claim 1, it is characterised in that：Group
The content range for dividing the macromolecule nonionic surfactant of (D) is 25~35%.
6. the environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth according to claim 1, it is characterised in that：Group
The macromolecule nonionic surfactant for dividing (D) is dimeric dibasic acid/APEO condensation polymer, and its preparation method is as follows：
A, ethyleneoxide addition polymerization prepares polyoxyethylene ether dimeric acid esters：Dimeric dibasic acid 565kg, hydrogen-oxygen are added into reactor
Change potassium 2.0kg, open and be heated with stirring to 150~170 DEG C, be evacuated to -0.08~-0.09MPa, be dehydrated 20 minutes, close vacuum
Valve, inflated with nitrogen is to 0.06MPa, then is evacuated to -0.08MPa, inflated with nitrogen, common 3 times repeatedly, denitrogen gas to pressure-fired, begins to add ring
Oxidative ethane, after question response is steady, 150 ± 5 DEG C of controlling reaction temperature, 0.2~0.3MPa of pressure, co-continuous addition oxirane
1500~3000kg, treat all to add, after kettle pressure drop to 0 gauge pressure, holding continues reaction 20 minutes, vacuumizes 15 under this condition
Minute, less than 70 DEG C are cooled to, acetic acid on the rocks adjusts pH to 6~7, discharging；
B, condensation polymerization prepares dimeric dibasic acid/APEO condensation polymer：Add into reactor dimeric dibasic acid 100kg, step (a)
Product polyoxyethylene ether dimeric 430~940kg of acid esters, the two mol ratio 1：1.2~1.5,0.5~1.0kg of composite catalyst, stir
Mix and be heated to 120 DEG C, be evacuated to gauge pressure≤- 0.09MPa, 160~180 DEG C of maintenance reaction temperature to substantially anhydrous abjection, after
Continuous dehydration half an hour, 70 DEG C are cooled to bottom discharge, obtains dimeric dibasic acid/APEO condensation polymer.
7. the environmentally friendly multiple hydrophilic finishing agent of polyolefm non-woven cloth according to claim 1, it is characterised in that：Group
The macromolecule nonionic surfactant for dividing (D) is dimeric dibasic acid/oleic acid or stearic acid monoglycerides APEO condensation polymer, and it is made
Preparation Method is as follows：
A, ethyleneoxide addition polymerization prepares oleic acid or stearic acid monoglycerides APEO：Into reactor add oleic acid or
Stearic acid monoglycerides 1kmol, potassium hydroxide 0.6kg, open and be heated with stirring to 130~150 DEG C, it is evacuated to -0.08~-
0.09MPa, it is dehydrated 20 minutes, closes vacuum valve, inflated with nitrogen is to 0.06MPa, then is evacuated to -0.08MPa, inflated with nitrogen, anti-altogether
It is multiple 3 times, denitrogen gas to pressure-fired, begin to add oxirane, after question response is steady, 140 ± 5 DEG C of controlling reaction temperature, pressure 0.2~
0.3MPa, co-continuous addition 26~52kmol of oxirane, treat all to add, after kettle pressure drop to 0 gauge pressure, keep under this condition
Continue reaction 20 minutes, vacuumize 15 minutes, be cooled to less than 70 DEG C, acetic acid on the rocks adjusts pH to 6~7, discharging；
B, condensation polymerization prepares dimeric dibasic acid/oleic acid or stearic acid monoglycerides APEO condensation polymer：Two are added into reactor
Polyacids 1kmol, the product oleic acid of step (a) or stearic acid monoglycerides 1.35~1.15kmol of APEO, composite catalyst
0.3~0.6%, 120 DEG C are heated with stirring to, is evacuated to gauge pressure≤- 0.09MPa, 160~180 DEG C of maintenance reaction temperature to base
This anhydrous abjection, continue to be dehydrated half an hour, be cooled to 70 DEG C with bottom discharge, obtain dimeric dibasic acid/oleic acid or stearic acid monoglycerides gather
Oxygen vinethene condensation polymer.
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| CN108611852A (en) * | 2018-05-08 | 2018-10-02 | 浙江理工大学 | A kind of ES fibers are without the multiple hydrophilic finish of silicon |
| JP6386206B1 (en) * | 2018-06-15 | 2018-09-05 | 竹本油脂株式会社 | Polyolefin-based nonwoven fabric treating agent, polyolefin-based synthetic fiber, and method for treating polyolefin-based synthetic fiber |
| CN109735967B (en) * | 2018-12-24 | 2021-03-23 | 常州市灵达化学品有限公司 | Dust-free paper fiber oiling agent |
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| EP1600532A1 (en) * | 2004-05-26 | 2005-11-30 | Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. | Hydrophilizing agent for polyolefin- and/or polyester-containing materials |
| CN102471967A (en) * | 2009-08-05 | 2012-05-23 | 三井化学株式会社 | Mixed fiber spunbond non-woven fabric and method for production and application of the same |
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| EP1600532A1 (en) * | 2004-05-26 | 2005-11-30 | Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. | Hydrophilizing agent for polyolefin- and/or polyester-containing materials |
| CN104593946A (en) * | 2008-05-29 | 2015-05-06 | 三井化学株式会社 | Mixed fiber spun bonded nonwoven fabric and use thereof |
| CN102471967A (en) * | 2009-08-05 | 2012-05-23 | 三井化学株式会社 | Mixed fiber spunbond non-woven fabric and method for production and application of the same |
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