CN105034517B - A kind of composite membrane - Google Patents

A kind of composite membrane Download PDF

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Publication number
CN105034517B
CN105034517B CN201510471249.5A CN201510471249A CN105034517B CN 105034517 B CN105034517 B CN 105034517B CN 201510471249 A CN201510471249 A CN 201510471249A CN 105034517 B CN105034517 B CN 105034517B
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Prior art keywords
woven fabrics
water repellent
composite membrane
electrostatic spinning
membrane
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CN105034517A (en
Inventor
张乃文
任杰
郁晓
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MAANSHAN TONGJIELIANG BIOLOGICAL MATERIAL Co.,Ltd.
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Shanghai Tong-Jie-Liang Biomaterials Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing

Abstract

Of the invention to provide a kind of composite membrane, the composite membrane includes the biomass polymers nano fibrous membrane positioned at upper strata and the water repellent SMS non-woven fabrics positioned at lower floor, the biomass polymers nano fibrous membrane and the non-woven fabric compounded formation composite membranes of the water repellent SMS；Fibre diameter in the biomass polymers nano fibrous membrane is 200 ~ 500nm, and the grammes per square metre of the water repellent SMS non-woven fabrics is 10 ~ 20 g/m2.The composite membrane is combined with each other by upper strata and primer, not only the effect of waterproof and breathable is more preferable, overcome the shortcomings that independent Electrospun nano-fibers film-strength is not high simultaneously, also be not in fracture under vigorous motion, while compound non-woven fabrics is its sensation more soft comfortable with human contact.

Description

A kind of composite membrane
Technical field
The present invention relates to polymer compound film field, and in particular to a kind of composite membrane of personal-care supplies counterdie.
Background technology
Current market sales of amenities counterdie is mostly PE making hole films, and its shortcoming is airtight, and for defending On raw articles for use, skin is directly contacted, certain stimulation is produced to skin, user is produced sense of discomfort, if using saturating Gas is good, and the non-woven fabrics non-stimulated to skin can not be accomplished to totally block oozing out for liquid, become health again as counterdie Industry is for a long time without the problem solved.Even if technical side of the PE making hole films compound nonwoven cloth as counterdie was had later Case, but the essence of PE film poor air permeabilities does not change really.
Patent CN200910306527.6 describes a kind of compound counterdie of sanitary napkin, be PE casting films by PUR or It is heat-sealable way with common non-woven fabric compounded into sanitary napkin counterdie, although employing funnel-form punching, PE films are in itself Material structure determines that its permeability can not reach satisfied effect all the time.
Patent CN201110309966 describes a kind of composite hyperfiltration membrane of modification of chitosan Electrospun nano-fibers, is By the way that chitosan after modified is a kind of high close coated in being mutually compounded to form in polymer electrospun film layer and with non-woven fabrics It is water-based, the excellent composite filtering film of permeability.But the counterdie of sanitary napkin necessarily requires complete water preventing ability, so simultaneously uncomfortable For sanitary goods industry.
The patent of invention that domestic applications number are 2014103395120 discloses a kind of preparation method of antibacterial nonwoven cloth, its Processing is carried out to non-woven fabrics using padding liquid and obtains a kind of non-woven fabrics with antibacterial effect, but this non-woven fabrics employs nanometer Silver, production cost is high, and its gas permeability cannot be guaranteed.The patent of invention that domestic applications number are 2012100926792 discloses one Kind moisture-inhibiting porous film, it includes the thermoplastic resin and filler boiling beyond polylactic acid based resin, polylactic acid based resin Stone, it is this porous film penetrability, flexibility, heat-resist, it is biodegradable, available for making sheet, pillowcase, sanitary napkin With the ground of the absorbent commodity such as paper nappy, but the gas permeability of this film still can not meet market needs.
The content of the invention
The defects of it is an object of the invention to overcome prior art, there is provided a kind of new ground for absorbent commodity The defects of composite membrane poor air permeability, degradability difference and leakproof fluidity difference.
In order to realize object above and other purposes, the present invention including following technical scheme by realizing：
A kind of composite membrane, the composite membrane are included positioned at the biomass polymers nano fibrous membrane on upper strata and positioned at lower floor Water repellent SMS non-woven fabrics, the biomass polymers nano fibrous membrane and the non-woven fabric compounded formation of the water repellent SMS are described compound Film；Fibre diameter in the biomass polymers nano fibrous membrane is 200~500nm, the grammes per square metre of the water repellent SMS non-woven fabrics For 10~20g/m2。
Preferably, the biomass polymers nano fibrous membrane is selected from polylactic acid nano fiber film, chitosan nano fiber One or more in film, fibroin nano fibrous membrane, sodium alginate nano fiber film and bamboo fibre nano fibrous membrane.
Preferably, the biomass polymers nano fibrous membrane is to be obtained using electrospinning process.
Preferably, the thickness of the biomass polymers nano fibrous membrane is 0.1~0.5mm.
Preferably, the fibre diameter of the water repellent SMS non-woven fabrics is 1~10 μm.
Preferably, the water repellent SMS non-woven fabrics is the SMS non-woven fabrics arranged by water repellent, and the water repellent makes Dosage is the 3~6% of the SMS non-woven weights.
The above-mentioned finishing technique for using water repellent to be arranged is using spray process or padding method.
Specifically, the technological process of spray process is：Spray → drying → bakes → washing → drying.
Specifically, the technological process of padding method is：Pad → drying → and bake → washing → drying.
Preferably, the SMS non-woven fabrics is polypropylene or polyester.
Preferably, the water repellent is selected from paraffin-aluminum soap, pyridine quaternary ammonium salt, melamine methylol derivative, stearic acid One or more in chromium complex and organosilicon.
The invention also discloses a kind of method for preparing composite membrane as described above, the described method comprises the following steps：
1) electrostatic spinning liquid is prepared：Biomass polymers are dissolved in organic solvent, stirs and electrostatic spinning liquid is made, it is described The mass concentration of electrostatic spinning liquid is 7~10wt%；The biomass polymers are selected from PLA, chitosan, fibroin, alginic acid One or more in sodium and bamboo fibre；
2) electrostatic spinning liquid in step 1) is used to carry out electrostatic spinning：The environment temperature of electrostatic spinning is 20~80 DEG C, Receiving plane is SMS non-woven fabrics, and the distance between electrostatic spinning spinning head and bottom SMS non-woven fabrics are 5~30cm, and feeding speed is 8~20ml/h, voltage are 5~30kV, and the transmission speed of the SMS non-woven fabrics is 0.5~2m/min.
It is polylactic acid nano fiber film as preferably technical scheme, a biomass polymers nano fibrous membrane, The biomass polymers are PLA, and electrostatic spinning liquid is PLA solution.
Preferably, the polylactic acid nano fiber film is to pass through electrostatic spinning technique by raw material spinning solution of PLA solution Obtain.
Preferably, the PLA solution is that PLA is dissolved in the solution formed in chloroform and acetone mixed solvent, described The number-average molecular weight of PLA is 10~200,000, and the volume ratio of the in the mixed solvent chloroform and acetone is 1~3:1.
Preferably, the concentration of the PLA solution is 5~10wt%.
Preferably, the electrostatic spinning technique is to be sprayed using 5~10ml/h extruded velocity under 15~20KV electric field Project polylactic acid nano fiber and carry out electrostatic spinning, the polylactic acid nano fiber is sprayed in forming composite membrane on SMS non-woven fabrics.
Preferably, the injecting time is at least 10min.
Preferably, the reception distance of the SMS non-woven fabrics is 10~20cm.
The invention also discloses purposes of the composite membrane as described above as the ground of absorbent commodity.
Heretofore described composite membrane upper strata is that the binary that electrostatic spinning obtains cooperates with interface biomass polymers Nanowire Film is tieed up, contains many beading in it, possesses super water repellency, can effectively prevent the seepage of liquid；Meanwhile the biomass on upper strata is gathered Compound nano fibrous membrane is superfine fibre network structure, and fibre diameter is nanoscale, and specific surface area is big, and permeability is very good, Excellent absorption property is provided simultaneously with, shows effective barrier to harmful liquid and gas, is made in the routine of waterproof and breathable With the characteristic that adds additional filtering outside.
The bottom of the composite membrane is the ultra-thin SMS non-woven fabrics of hydrophobic permeable, is typically used as the gusset that blocks water of amenities, It is compound by spunbond-melt blown-spunbond three-decker, the effect of hydrophobic permeable is not only ensure that, while in the premise of ultrathin Under also improve the tensile strength of material.
The composite membrane is combined with each other by upper strata and primer, and not only the effect of waterproof and breathable is more preferable, overcomes simultaneously The shortcomings that independent Electrospun nano-fibers film-strength is not high, is also not in fracture under vigorous motion, while institute Compound non-woven fabrics is its sensation more soft comfortable with human contact.
The composite membrane integral material is biomass polymers, security, good with human body skin compatibility, and raw material naturally comes Source, product can be biodegradable, can realize the circulation in nature, therefore are preferable Green Polymer Materials, overcome Existing sanitary napkin is difficult to the shortcomings that degraded on current market.
Brief description of the drawings
Fig. 1 is the electrostatic spinning production process schematic diagram of heretofore described composite membrane.
Fig. 2 is the structural representation of heretofore described composite membrane.
Reference is as follows in Fig. 1~2：
1 is syringe pump；
2 be biomass polymers solution；
3 be high-tension electricity；
4 be syringe needle drop；
5 be SMS non-woven fabrics；
6 be biomass polymers nanofiber；
7 be biomass polymers nano fibrous membrane.
Embodiment
The present invention is expanded on further with reference to embodiment.It should be understood that embodiment is merely to illustrate the present invention, and it is unrestricted The scope of the present invention.
The process schematic representation of electrostatic spinning technique is as shown in Figure 1 in the embodiment of the present invention.The biomass prepared is polymerize Thing solution is added in syringe pump, and using SMS non-woven fabrics as electrostatic spinning receiving plane, after leading to upper high-tension electricity, syringe pump is according to certain Speed extrudes biomass polymers solution, and it forms syringe needle drop in syringe pump syringe needle, stretches to form biomass and gather through high-voltage field Compound nanofiber falls the formation biomass polymers nano fibrous membrane on SMS non-woven fabrics.
The average pore size of the composite membrane obtained in the present embodiment is to test to obtain using ASTMD6767-02 methods, resistance to hydrostatic Pressure value is to test to obtain using the methods of GB/T 4744, and air penetrability is to test to obtain using GB/T5453 methods.
Embodiment 1
The present embodiment carries out electrostatic spinning using 7wt% PLA solution, in the solvent in PLA solution chloroform and The volume ratio of acetone is 2:1, the molecular weight of PLA is 140000, and voltage is 18KV, extruded velocity 8ml/ in electrostatic spinning H, received using SMS non-woven fabrics, it is 15cm to receive distance, and the environment temperature of electrostatic spinning is 60 DEG C, the biography of the SMS non-woven fabrics Defeated speed is 1.5m/min.
SMS non-woven fabrics is arranged by organosilicon water repellent in the present embodiment, and the usage amount of organosilicon water repellent is institute State the 3% of the quality of SMS non-woven fabrics.
Water repellent described in the present embodiment is organosilicon water repellent.
Arranged described in the present embodiment to be arranged using spray process.
The grammes per square metre of the SMS non-woven fabrics is 10g/m2.The material of the SMS non-woven fabrics is polypropylene material.
The fibre diameter of the water repellent SMS non-woven fabrics is 1~10 μm.
The average diameter of the polylactic acid nano fiber obtained in the present embodiment is 355nm.
The process schematic representation of electrostatic spinning technique is as shown in Figure 1.
After tested, the average pore size of the composite membrane obtained in the present embodiment is 4.41 μm, and resistance to hydrostatic pressure value is 700mm, thoroughly Gas rate is 6.74mm/s.
Embodiment 2
Composite membrane comprises the following steps preparation method in the present embodiment：
1) electrostatic spinning liquid is prepared：Biomass polymers are dissolved in organic solvent, stirs and electrostatic spinning liquid is made, it is described The mass concentration of electrostatic spinning liquid is 10%；The biomass polymers are selected from 20% fibroin and 80% PLA is placed in six In fluorine isopropanol HFIP；Stirred 24 hours at 25 DEG C of constant temperature and obtain uniform electrostatic spinning liquid；
2) electrostatic spinning liquid in step 1) is used to carry out electrostatic spinning：The environment temperature of electrostatic spinning is 25 DEG C, is received Face is SMS non-woven fabrics, and the distance between electrostatic spinning spinning head and bottom SMS non-woven fabrics are 12cm, feeding speed 8ml/h, Voltage is 16kV, and the transmission speed of the SMS non-woven fabrics is 1.5m/min.The average diameter of the composite membrane eventually formed is 464nm。
Organosilicon water repellent described in the present embodiment is pyridine quaternary ammonium salt.
Arrangement dips technique for use and arranged described in the present embodiment.
The grammes per square metre of the SMS non-woven fabrics is 15g/m2.The material of the SMS non-woven fabrics is polyester.
The fibre diameter of the water repellent SMS non-woven fabrics is 1~10 μm.
After tested, the average pore size of the composite membrane is 10.59 μm, and resistance to hydrostatic pressure value is 579mm, air penetrability 8.63mm/ s。
Embodiment 3
Composite membrane comprises the following steps preparation method in the present embodiment：
A prepares electrostatic spinning liquid：Biomass polymers are dissolved in organic solvent, stirs and electrostatic spinning liquid is made, it is described The mass concentration of electrostatic spinning liquid is 8%；The biomass polymers are selected from 30% bamboo fibre and 70% PLA is placed in In hexafluoroisopropanol HFIP；Stirred 24 hours at 25 DEG C of constant temperature and obtain uniform electrostatic spinning liquid；
B uses the electrostatic spinning liquid in step 1) to carry out electrostatic spinning：The environment temperature of electrostatic spinning is 50 DEG C, receiving plane For SMS non-woven fabrics, the distance between electrostatic spinning spinning head and bottom SMS non-woven fabrics are 25cm, feeding speed 15ml/h, electricity Press as 16kV, the transmission speed of the SMS non-woven fabrics is 2m/min.
The average diameter of the composite membrane eventually formed is 298nm.
Organosilicon water repellent described in the present embodiment is stearate chromium complex.
Arranged described in the present embodiment to be arranged using spray process.
The grammes per square metre of the SMS non-woven fabrics is 20g/m2.The material of the SMS non-woven fabrics is polyester.
The fibre diameter of the water repellent SMS non-woven fabrics is 1~10 μm.
After tested, the average pore size of the composite membrane is 15.43 μm, and resistance to hydrostatic pressure value is 436mm, air penetrability 9.78mm/ s。
Embodiment 4
Composite membrane comprises the following steps preparation method in the present embodiment：
A prepares electrostatic spinning liquid：Biomass polymers are dissolved in organic solvent, stirs and electrostatic spinning liquid is made, it is described The mass concentration of electrostatic spinning liquid is 9wt%；The biomass polymers are selected from 10% chitosan and 90% PLA is put In hexafluoroisopropanol HFIP；Stirred 24 hours at 25 DEG C of constant temperature and obtain uniform electrostatic spinning liquid；
B uses the electrostatic spinning liquid in step 1) to carry out electrostatic spinning：The environment temperature of electrostatic spinning is 50 DEG C, receiving plane For SMS non-woven fabrics, the distance between electrostatic spinning spinning head and bottom SMS non-woven fabrics are 20cm, feeding speed 20ml/h, electricity Press as 20kV, the transmission speed of the SMS non-woven fabrics is 0.5m/min.
The average diameter of the composite membrane eventually formed is 353nm.
Organosilicon water repellent described in the present embodiment is paraffin-aluminum soap.
Arrangement dips technique for use and arranged described in the present embodiment.
The grammes per square metre of the SMS non-woven fabrics is 18g/m2.The material of the SMS non-woven fabrics is polypropylene.
The fibre diameter of the water repellent SMS non-woven fabrics is 1~10 μm.
After tested, the average pore size of the composite membrane is 8.31 μm, and resistance to hydrostatic pressure value is 834mm, air penetrability 6.71mm/s.
The structure of composite membrane schematic diagram obtained in embodiment 1~4 is as shown in Figure 2.
It is described above, only presently preferred embodiments of the present invention, it is not any to the present invention in form and substantial limitation, It should be pointed out that for those skilled in the art, on the premise of the inventive method is not departed from, can also make Some improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art, Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more Dynamic, modification and the equivalent variations developed, it is the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention The variation, modification and evolution for any equivalent variations that above-described embodiment is made, still fall within the scope of technical scheme It is interior.

Claims (5)

  1. A kind of 1. composite membrane, it is characterised in that：The composite membrane include positioned at upper strata biomass polymers nano fibrous membrane and Positioned at the water repellent SMS non-woven fabrics of lower floor, the biomass polymers nano fibrous membrane and the non-woven fabric compounded formation of water repellent SMS The composite membrane；Fibre diameter in the biomass polymers nano fibrous membrane is 200~500nm, the water repellent SMS nonwovens The grammes per square metre of cloth is 10~20g/m2；The SMS non-woven fabrics is polypropylene or polyester；
    The biomass polymers nano fibrous membrane is selected from polylactic acid nano fiber film, chitosan nano fiber membrane, fibroin nanometer One or more in tunica fibrosa, sodium alginate nano fiber film and bamboo fibre nano fibrous membrane；
    The biomass polymers nano fibrous membrane is to be obtained using electrospinning process；
    The water repellent SMS non-woven fabrics is the SMS non-woven fabrics arranged by water repellent, and the usage amount of the water repellent is described The 3~6% of SMS non-woven weights；
    The water repellent be selected from paraffin-aluminum soap, pyridine quaternary ammonium salt, melamine methylol derivative, stearate chromium complex and One or more in organosilicon.
  2. 2. composite membrane as claimed in claim 1, it is characterised in that：The thickness of the biomass polymers nano fibrous membrane is 0.1 ~0.5mm.
  3. 3. composite membrane as claimed in claim 1, it is characterised in that：The fibre diameter of the water repellent SMS non-woven fabrics is 1~10 μm.
  4. 4. a kind of method for preparing the composite membrane as described in claims 1 to 3 is any, the described method comprises the following steps：
    1) electrostatic spinning liquid is prepared：Biomass polymers are dissolved in organic solvent, stirs and electrostatic spinning liquid, the electrostatic is made The mass concentration of spinning solution is 7~10%；The biomass polymers are selected from PLA, chitosan, fibroin, sodium alginate and bamboo One or more in fiber；
    2) electrostatic spinning liquid in step 1) is used to carry out electrostatic spinning：The environment temperature of electrostatic spinning is 20~80 DEG C, is received Face is SMS non-woven fabrics, and the distance between electrostatic spinning spinning head and bottom SMS non-woven fabrics are 5~30cm, feeding speed is 8~ 20ml/h, voltage are 5~30kV, and the transmission speed of the SMS non-woven fabrics is 0.5~2m/min.
  5. 5. purposes of the composite membrane as the ground of absorbent commodity as described in claims 1 to 3 is any.
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CN105437667A (en) * 2016-01-08 2016-03-30 清华大学 Preparation method of composite base material for facial masks
CN107028250A (en) * 2017-04-25 2017-08-11 漯河医学高等专科学校 Antibacterial mask filter disc
KR101975118B1 (en) * 2017-11-30 2019-08-28 주식회사 한일타포린 cargo cover for pallet of air freight
CN109825955B (en) * 2019-02-03 2021-09-17 南通纺织丝绸产业技术研究院 Antibacterial and anti-allergic paper diaper for adults and preparation method thereof
CN110589242A (en) * 2019-08-02 2019-12-20 中山火炬职业技术学院 Packaging method of breakable solid
CN110589067A (en) * 2019-08-02 2019-12-20 中山火炬职业技术学院 Moisture-proof packaging technology for solid
CN113350215A (en) * 2021-06-08 2021-09-07 诺斯贝尔化妆品股份有限公司 Interlayer composite dry type nano fiber skin care product and preparation method thereof
CN113288595A (en) * 2021-06-30 2021-08-24 福建恒安集团有限公司 High-permeability basement membrane for paper diapers and processing technology thereof

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PL1751338T3 (en) * 2004-04-19 2011-04-29 Procter & Gamble Fibers, nonwovens and articles containing nanofibers produced from high glass transition temperature polymers
JP5009100B2 (en) * 2007-08-31 2012-08-22 日本バイリーン株式会社 Extra fine fiber nonwoven fabric, method for producing the same, and apparatus for producing the same
JP5563817B2 (en) * 2008-12-26 2014-07-30 花王株式会社 Method of attaching nanofiber sheet
CN103388265B (en) * 2012-05-08 2016-08-03 北京服装学院 A kind of waterproof moisture-permeable multifunctional composite micro/nano fabric and preparation method thereof

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Assignee: Hangzhou Dehong Technology Co.,Ltd.

Assignor: MAANSHAN TONGJIELIANG BIOLOGICAL MATERIAL CO.,LTD.

Contract record no.: X2022330000058

Denomination of invention: A composite membrane

Granted publication date: 20180306

License type: Common License

Record date: 20220318