CN104559095A - Resin composition for preparing micro-porous thin film and micro-porous thin film - Google Patents
Resin composition for preparing micro-porous thin film and micro-porous thin film Download PDFInfo
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Abstract
The invention relates to a resin composition for preparing a micro-porous thin film and the prepared micro-porous thin film. The composition comprises the following components in parts by weight: 20-80 parts of polylactic resin A, 5-50 parts of a resin component B which is incompatible with polylactic acid and 5-50 parts of filler C, wherein the percentage by weight of the filler C which is fully in the phase B or partially in the phase B is as follows: C% is greater than (0.9*B%+10%) and B% is the volume percentage of B in the resin composition. The water vapor permeability of the micro-porous thin film prepared from the resin composition is higher than the water vapor permeability of a thin film where the filler is averagely distributed. The resin composition for preparing the micro-porous thin film provided by the invention can be used for preparing the micro-porous thin film and can be used in the field of hygienic products, building materials and the like.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of resin combination for the preparation of micro-porous membrane, and micro-porous membrane of preparing of resin combination thus.
Background technology
The micro-porous membrane of so-called Waterproof Breathable, refer to that polymkeric substance is with after filler mixing, obtains former film by the method such as curtain coating or blowing, then through unidirectional or two-way stretching, make filler and polymkeric substance or between polymkeric substance and polymkeric substance, interfacial separation occur, film being produced Voiding.The micro-porous membrane of Waterproof Breathable is used on the disposable products such as nursing materials, physiological hygiene articles for use, paper diaper.Described polymkeric substance is generally polyolefine, especially polyethylene or polypropylene.Polyolefin polymers non-degradable, and be raw material with oil, so this type of film has a certain impact to environment.As patent documentation CN1204167C the air-permeating film that discloses, comprise polypropylene copolymer and filler.
Along with the environmental protection theory of the public is strengthened, more and more praised highly based on the plastics film of biological degradation and biological material.Poly(lactic acid) is a kind of Biodegradable polyester, and the micro-porous membrane containing this polymkeric substance is referred, can be applied in the field such as hygiene care, medical treatment.But due to the gap of its performance and conventional polyolefins material, its Water Vapour Permeability is general lower.
CN 201310185870.6 adopts the method for particle-filled-stretching, a kind of micro-porous membrane containing biological degradation polyalcohols such as poly(lactic acid) is provided, the area of the surface holes of diameter within the scope of 0.2 ~ 7 μm accounts for the 0.5%-15% of total surface area, fastness to water is greater than 800mm, and Water Vapour Permeability is greater than 1000g/ (m
2day), firm softness is less than 40mm.Can be used as moisture permeable waterproof film for health care field.
Summary of the invention
Poly(lactic acid) is due to the defect in its processing characteristics, usual needs and other resins carry out composite use, and due to the existence be separated, other resins being in disperse phase can not fully be stretched, this part resin can have certain iris action to water vapour, and the film Water Vapour Permeability causing it to make is lower.
For above-mentioned defect of the prior art, the invention provides a kind of resin combination for the preparation of micro-porous membrane, it contains polylactic resin, one or more are with the inconsistent resin of poly(lactic acid) and filler, and by Fillers selection is dispersed in the described inconsistent resin-phase of same poly(lactic acid), or be dispersed in poly(lactic acid) with on the interface of incompatible resin, make the micro-porous membrane prepared by said composition have very high water vapour permeability, moisture-inhibiting reaches 1500g/(m
2d) more than.
Specifically, the invention provides a kind of resin combination for the preparation of micro-porous membrane, the component containing, for example lower parts by weight: polylactic resin A:20-80 weight part; With poly(lactic acid) inconsistent resin Composition B:5-50 weight part; Filler C:5-50 weight part; Wherein, the filler C completely in B phase or partly in B phase accounts for the per-cent C%>(0.9 × B%+10% of filler C), wherein B% is the percent by volume of B shared by resin combination.
For the preparation of the resin combination of micro-porous membrane in the present invention, be preferably the component containing, for example lower parts by weight: polylactic resin A:40-75 weight part; With poly(lactic acid) inconsistent resin Composition B:10-40 weight part; Filler C:10-45 weight part.Too much filler easily causes film strength to decline, and very few filler can cause film void content low, affects Water Vapour Permeability.
Described polylactic resin (A) is one or more in the multipolymer of poly(lactic acid) or lactic acid and hydroxycarboxylic acid.The molecular structure of preferred poly(lactic acid) is, the molecular structure be made up of 80-100mol% and the respective enantiomorph 0-20mol% of L lactic acid or D lactic acid.Described hydroxycarboxylic acid, can list oxyacetic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxycaproic acid or hydroxyheptanoic acid etc., preferred oxyacetic acid, hydroxypentanoic acid or hydroxycaproic acid.In addition, the multipolymer of described lactic acid and hydroxycarboxylic acid is made up of the 85-100mol% of L lactic acid or D lactic acid and hydroxycarboxylic acid unit 0-15mol%.Above-mentioned polylactic resin can select the material of desired structure as raw material among one or both L lactic acid or D lactic acid and hydroxycarboxylic acid, and is obtained by dehydrating polycondensation.Preferably, can from the rac-Lactide of the cyclic dimer as lactic acid, as the material selecting desired structure the glycollide of the cyclic dimer of oxyacetic acid and caprolactone etc., be obtained by ring-opening polymerization.The Study of Meso-Lactide having the cyclic dimer of L lactic acid and L rac-Lactide, the cyclic dimer of D lactic acid and D rac-Lactide, D lactic acid and L lactic acid to carry out cyclic dimer and obtain in rac-Lactide and the racemic mixture of D rac-Lactide and L rac-Lactide and DL rac-Lactide.Any one rac-Lactide can be used in the present invention.But, the preferred D rac-Lactide of main raw material or L rac-Lactide.
About the molecular weight of polylactic resin (A), there is no particular limitation, but consider from the angle improving molding processibility and mechanical property, preferable weight-average molecular weight 50,000 ~ 500,000, and further preferably 80,000-30 ten thousand.
Described polylactic resin A is the composition of crystalline polylactic acid, amorphism poly(lactic acid) or crystalline polylactic acid and amorphism poly(lactic acid).Be preferably the composition of amorphism poly(lactic acid) or amorphism poly(lactic acid) and crystalline polylactic acid.Be more preferably the composition of amorphism poly(lactic acid) and crystalline polylactic acid, wherein amorphism poly(lactic acid) weight content is preferred higher than 50% further.
Be preferably in described polylactic resin A also containing softening agent D.
Because poly(lactic acid) rigidity is large, there is the feature of difficult processing, in its course of processing, add softening agent, its pliability can be improved and improve its processing characteristics.
Described softening agent D be preferably in the multipolymer of the multipolymer of polyoxyethylene glycol, polypropylene glycol, lactic acid oligomer, rac-Lactide oligopolymer, ethylene oxide/propylene oxide multipolymer, citrate triethyl, tributyl citrate, acetyl triethyl citrate, tributyl acetylcitrate, Coronex, polycaprolactone and poly(lactic acid), poly-succinic fourth diester and poly(lactic acid), poly-alkyl diol and the multipolymer of lactic acid or the multipolymer of Viscotrol C and lactic acid one or several.
The inconsistent resin Composition B of described same poly(lactic acid) has thermoplastic fluoropolymer resin, provides film with suitable flexibility.
From the view point of flexibility and the processing characteristics of improving film further, described same poly(lactic acid) inconsistent resin Composition B is preferably polyolefins, polyurethanes, vinyl acetate class, one or more in polyamide-based, polyoxymethylene class, polynitriles class, aliphatic polyester series, aromatic polyester class, aliphatic-aromatic copolyester class, aliphatic polycarbonate class or aromatic copolycarbonate class that second-order transition temperature is less than 40 DEG C.
Described polyolefins is: one or more in polyethylene, polypropylene or polybutene.
Described polyurethanes is: thermoplastic polyurethane.
Described vinyl acetate class is: one or more in polyvinyl acetate (PVA) and ethylene-vinyl acetate copolymer.
Described is polyamide-based: obtained by interior acid amide ring-opening polymerization, or the polymkeric substance obtained by diamine and diprotic acid polycondensation etc.
Described polyoxymethylene class is: the homopolymer obtained by oxymethylene polymerization.
Described polynitriles class is: polyacrylonitrile, or the polymkeric substance of other nitrile.
Described fatty acid polyester class carries out polycondensation or ring-opening polymerization by one or more of aliphatic dicarboxylic acid (comprising its derivative) and aliphatic diol (comprising its derivative), hydroxycarboxylic acid (comprising its derivative) or lactone.
Described aromatic polyester carries out polycondensation or ring-opening polymerization by one or more of aromatic dicarboxylic acid (comprising its derivative) and aromatic series (or aliphatics) glycol (comprising its derivative), hydroxycarboxylic acid (comprising its derivative) or lactone.
Described aliphatic-aromatic copolyester class adds one or more aromatic series aliphaticdicarboxylic acid (comprising its derivative) monomer in the monomer of the above-mentioned aliphatic polyester of composition, carries out polycondensation.
Described aliphatic polycarbonate class be comprise-O-R-O-CO-structural unit resin.Wherein, R represent carbonatoms 2 ~ 20 have substituent alkylidene group or carbonatoms 6 ~ 20 have in substituent cycloalkylidene one or more.
Described aromatic copolycarbonate class is the resin comprising-O-R-O-CO-structural unit.Wherein R represent containing phenyl ring or condensed ring have in substituent aromatic substituents one or more.
The inconsistent resin Composition B of described same poly(lactic acid) more preferably polyethylene, polypropylene, polybutene, polyvinyl chloride, polyacrylonitrile, urethane, polymethylmethacrylate, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polystyrene, polyvinyl acetate (PVA), ethylene-vinyl acetate copolymer, poly butyric ester, PHBV, polyhydroxybutyrate capronate, poly butylene succinate, poly-succinic tetramethylene adipate, polycaprolactone, poly terephthalic acid tetramethylene adipate, poly terephthalic acid hexanodioic acid propylene glycol ester, poly terephthalic acid succinic acid-butanediol ester, poly-ethylene carbonate, polypropylene carbonate, or one or more in polymerized thylene carbonate cyclohexyl.
Described filler C refers to mineral filler or/and organic filler.
Mineral filler, glass fibre can be listed particularly, fibrous magnesium silicate, carbon fiber, graphite fibre, steel fiber, potassium titanate crystal whisker, aluminium borate whisker, magnesium system whisker, silicon system whisker, wollastonite, sepiolite, asbestos, slag fibre, xonotlite, ellestadite, gypsum fiber, silica fiber, silica/alumina fiber, Zirconium oxide fibre, boron nitride fibre, one or more in the fibrous inorganic filler such as silicon nitride fiber or boron fibre, or glass flake, non-bloating tendency mica, bloating tendency mica, graphite, tinsel, ceramic beads, talcum, clay, mica, sericite, zeolite, wilkinite, vermiculite, polynite, rhombspar, kaolin, micro mist silicic acid, Feldspar Powder, potassium titanate, fine hollow glass ball, calcium carbonate, magnesiumcarbonate, calcium sulfate, titanium dioxide, silicon oxide, gypsum, novaculite, one or more in the sheet such as dawsonite or carclazyte or granular inorganic filler.
Organic filler, can list one or more in the organic synthetic fibers such as the animal fiber such as vegetative fiber, wool fiber, Kevlar or aromatic polyester fibres such as starch, Mierocrystalline cellulose, sisal fibers or bamboo fibers particularly.
One or more more preferably in zeolite powder, talcum powder, mica powder, titanium dioxide, silicon-dioxide, calcium carbonate, calcium sulfate, polynite, ceramic microsphere, starch, Mierocrystalline cellulose, vegetative fiber, animal fiber or organic synthetic fibers of filler C.
Above-mentioned filler (C) can carry out the surface treatment of arbitrary form, to strengthen it with the interfacial adhesion between resin.
In described filler (C), then one or more in further preferably calcium carbonate, zeolite powder, talcum powder, mica powder, titanium dioxide, silicon-dioxide, calcium sulfate or polynite.Most preferably be calcium carbonate.
Described filler (C) though median size nonessential, be good with 0.01 ~ 10 μm.
Described resin combination, for the preparation of micro-porous membrane, in order to improve the flexibility of micro-porous membrane further, also contains the expanding material (E) of parts by weight 0.1-5 weight part.Expanding material (E) be in molecular structure with two or more can with one or more in the compound of the response type functional group of carboxyl or hydroxyl reaction, described response type functional group is one or more in epoxy-functional, isocyanate functional group, carbodiimide functional group, anhydride functional group, silane functional, Zuo Lin functional group or phosphorous acid ester functional group.By these response type functional groups with the carboxyl of poly(lactic acid) or hydroxyl reaction, increase-volume can be carried out to poly(lactic acid).
Specifically, expanding material (E) can be tolylene diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, Lysine triisocyanate, γ-glycidyl ether oxygen propyl trimethoxy silicane, polymerization charing diimine, ethylene-acrylate-maleic anhydride terpolymer or with one or more in the acrylic polymer of epoxy-functional.
In addition, resin combination for the preparation of micro-porous membrane of the present invention, need according to practical application, one or more in the auxiliary agents such as appropriate thermo-stabilizer, end-capping reagent, anti ultraviolet agent, fire retardant, nucleator, lubricant, static inhibitor or tinting material can be added in addition.
The not special requirement of kind for each auxiliary agent, can use various known commodity.Consider from the adaptable angle with biological degradation polyalcohol, one or more in the preferred hindered phenol based compound of thermo-stabilizer, phosphorous acid ester based compound or thioether based compound; One or more in end-capping reagent preferred isocyanate based compound, carbodiimide based compound or azoles quinoline based compound; One or more in the preferred benzophenone based compound of anti ultraviolet agent, benzotriazole based compound, aromatic series benzoic ether based compound, oxanilide based compound, cyanoacrylate based compound or hindered amine based compound; One or more in the antimony compounds such as halogen based compound, ANTIMONY TRIOXIDE SB 203 99.8 PCT of fire retardant preferably containing bromine or chlorine, inorganic hydrate or phosphorus compound etc.; One or more in nucleator preferred aliphat acid amides based compound, aliphatic ester compound or talcum powder; One or more preferably in low white oil, paraffin or aliphatic amide based compound of lubricant.
The all or part of increase that can cause B phase apparent size in the middle distribution of B phase of filler C, so-called apparent size refers to the section obtaining resin combination by methods such as sections, tick the profile of B with pen after, utilize image processing software Image J 1.46 to calculate the sectional area of all B phases, recycle the apparent size of mean value as B phase of the circular diameter of the difference correspondence that this sectional area calculates.The apparent size of the phase of the inconsistent resin Composition B component of described same poly(lactic acid) is optimized for 0.5 μm-50 μm, is more optimized for its diameter 1 μm-20 μm, is optimized for diameter 2 μm-15 μm further.The apparent size of B phase increases the raising being conducive to the film Water Vapour Permeability obtained, but the apparent size increase of B phase can reduce the physicals of film.
The present invention also provides a kind of by the described micro-porous membrane prepared for the preparation of the resin combination of micro-porous membrane.
By micro-porous membrane that the present invention prepares, its Water Vapour Permeability is at 1500-4000g/(m
2d).
The present invention is not particularly limited for the preparation method of film, can adopt film-forming method of the prior art.Such as: by melt blending by after each component mixing, make former film through blowing or curtain coating, then obtain through unidirectional or two-way stretch.
Resin combination for the preparation of micro-porous membrane of the present invention, may be used for preparing micro-porous membrane, may be used for sanitary product, the fields such as material of construction.Due to the inclined Entropy density deviation of particle filled composite, make it in drawing process, two-phase resin can better be separated, and also better can produce hole with in the inconsistent resin-phase of poly(lactic acid), and the micro-porous membrane obtained by it has the high feature of Water Vapour Permeability.
Embodiment
By following examples, the present invention is described in more detail, but described embodiment is not construed as limiting the invention.
The testing method used in embodiment and comparative example is as follows:
Thickness: use instrument company 7050 of Sanyo type thickness gauge to measure, get the mean value of 9 data.
Weight-average molecular weight: use gel permeation chromatography, take chloroform as moving phase, measure 3 times, average.
Filler C defines position: observe resin combination section with TEM, general poly(lactic acid) A and with the inconsistent resin B of poly(lactic acid) and filler C, observes under the tem and presents different contrasts, distinguish the position of C with this.The methods such as known dyeing can be utilized to improve its contrast gradient for the resin close with poly(lactic acid) contrast.
The calculating of B%: B% is the percent by volume of B shared by resin combination, first utilizes the density p of resin combination
ctcalculate m
ctthe volume of the composition of weight part, the density p of recycling B
bcalculate m
ctpart volume corresponding to resin combination, namely the ratio of the volume of B and the volume of resin combination is B%, and calculation formula is as follows:
The per-cent C% of all or part of C in B phase: with TEM, resin combination section is observed as stated above, 5, the photo of random shooting different positions enlargement ratio 1000 times, tick the profile of B and filler C with pen after, calculate the area S of filler C and all or part of area S at the C of B phase respectively with image processing software ImageJ 1.46r
c, Sc obtains C% divided by S.
The apparent diameter of B: the section obtaining resin combination by methods such as sections, tick the profile of B with pen after, utilize image processing software Image J 1.46 to calculate the sectional area of all B phases, recycle the apparent size of mean value as B phase of the circular diameter of the difference correspondence that this sectional area calculates.
Rate of perviousness: based on JIS Z0208:1976, temperature 25 DEG C, humidity 90%.Measure 3 times, average.
Fastness to water: based on JIS L1092:2009, A method.Measure 3 times, average.
The raw material used in embodiment and comparative example is as follows:
< polylactic resin > (A)
A-1: poly(lactic acid), 4032D, Natureworks company of the U.S..
A-2: poly(lactic acid), 4060D, Natureworks company of the U.S..
< and the inconsistent resin > (B) of poly(lactic acid)
B-1: poly butylene succinate, Bionolle 1020, Japanese Showa polymer company.
B-2: polyhydroxybutyrate-hydroxyl valerate, ENMAT Y1000P, Ningbo Tianan Biological Material Co., Ltd..
B-3: poly terephthalic acid tetramethylene adipate, Ecoflex 7011, BASF Corp. of Germany.
B-4: polypropylene carbonate, BioCO2 100, Inner Mongol Meng Xi new and high technology group company.
< filler > (C)
C-1: calcium carbonate, particle diameter 3.6-5.0 μm, fine powder Co., Ltd. altogether of Japan three.
C-2: talcum powder, particle diameter 3.5-5.5 μm, Haicheng Xinda Mining Co., Ltd..
C-3:5A zeolite powder, Shanghai zeolite molecular sieve company.
< softening agent > (D)
D-1: tributyl acetylcitrate, Jiangsu Leimeng Chemical Industry Science and Technology Co., Ltd.
D-2: polypropylene glycol, number-average molecular weight 2000, Jiangsu Hai'an Petrochemical Plant.
D-3: PLA-PEG-PLA triblock copolymer, manufactures according to the embodiment 1 of CN200810018621.7.
< expanding material > (E)
E-1: ethylene/methyl acrylate/glycidyl methacrylate copolymer, Lotader
aX8900, French Arkema company.
E-2: multi-epoxy functional group cinnamic acrylic ester oligopolymer, Joncyrl
aDR 4368, BASF Corp. of Germany.
E-3: diphenylmethanediisocyanate, BASF Corp. of Germany.
Embodiment 1-9:
By the proportioning that table 1 is listed, carry out granulation with twin screw extruder, extrusion temperature 160-220 DEG C.Then, by single screw extrusion machine blowing, the former film that thickness is 80 μm is prepared.Blow temperatures 180-200 DEG C.And then at 85 DEG C, former film is carried out to the two-way stretch of 3.5 × 3.5 times, then, the film of gained is carried out to the test of various performance, the results are shown in Table 1.
Table 1 (unit: weight part)
Table 1(continues) (unit: weight part)
Claims (11)
1. for the preparation of a resin combination for micro-porous membrane, it is characterized in that: the component containing, for example lower parts by weight: polylactic resin A:20-80 weight part; With poly(lactic acid) inconsistent resin Composition B:5-50 weight part; Filler C:5-50 weight part; Wherein, the filler C completely in B phase or partly in B phase accounts for the per-cent C%>(0.9 × B%+10% of filler C), wherein B% is the percent by volume of B shared by resin combination.
2. the resin combination for the preparation of micro-porous membrane according to claim 1, is characterized in that: the component containing, for example lower parts by weight: polylactic resin A:40-75 weight part; With poly(lactic acid) inconsistent resin Composition B:10-40 weight part; Filler C:10-45 weight part.
3. the resin combination for the preparation of micro-porous membrane according to claim 1, is characterized in that: described polylactic resin A is the composition of amorphism poly(lactic acid) or amorphism poly(lactic acid) and crystalline polylactic acid.
4. the resin combination for the preparation of micro-porous membrane according to claim 3, is characterized in that: also containing softening agent D in described polylactic resin A.
5. the resin combination for the preparation of micro-porous membrane according to claim 4, is characterized in that: described softening agent D be selected from polyoxyethylene glycol, polypropylene glycol, lactic acid oligomer, rac-Lactide oligopolymer, ethylene oxide/propylene oxide multipolymer, citrate triethyl, tributyl citrate, acetyl triethyl citrate, tributyl acetylcitrate, sorbitol ester, polycaprolactone/copolymer of poly lactic acid, poly-succinic fourth diester/copolymer of poly lactic acid, poly-alkyl diol/lactic acid copolymer or Viscotrol C/lactic acid copolymer one or several.
6. the resin combination for the preparation of micro-porous membrane according to claim 1, it is characterized in that: the inconsistent resin Composition B of described same poly(lactic acid) is selected from polyethylene, polypropylene, polybutene, polyvinyl chloride, polyacrylonitrile, urethane, polymethylmethacrylate, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polystyrene, polyvinyl acetate (PVA), ethylene-vinyl acetate copolymer, poly butyric ester, PHBV, polyhydroxybutyrate capronate, poly butylene succinate, poly-succinic tetramethylene adipate, polycaprolactone, poly terephthalic acid tetramethylene adipate, poly terephthalic acid hexanodioic acid propylene glycol ester, poly terephthalic acid succinic acid-butanediol ester, poly-ethylene carbonate, polypropylene carbonate, or one or more in polymerized thylene carbonate cyclohexyl.
7. the resin combination for the preparation of micro-porous membrane according to claim 1, is characterized in that: described filler C is one or more in zeolite powder, talcum powder, mica powder, titanium dioxide, silicon-dioxide, calcium carbonate, calcium sulfate, polynite, ceramic microsphere, starch, Mierocrystalline cellulose, vegetative fiber, animal fiber or organic synthetic fibers.
8. the resin combination for the preparation of micro-porous membrane according to any one of claim 1-7, is characterized in that: the diameter with the phase of the inconsistent resin Composition B component of poly(lactic acid) is 0.5 μm-50 μm.
9. the micro-porous membrane prepared for the preparation of the resin combination of micro-porous membrane according to any one of claim 1-7.
10. one kind by the micro-porous membrane prepared for the preparation of the resin combination of micro-porous membrane according to claim 8.
11. micro-porous membranes according to claim 10, is characterized in that: its Water Vapour Permeability is at 1500-4000g/(m
2d).
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