CN104086777B - PLA (poly lactic acid) modified material and preparation method thereof - Google Patents
PLA (poly lactic acid) modified material and preparation method thereof Download PDFInfo
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- CN104086777B CN104086777B CN201410310466.1A CN201410310466A CN104086777B CN 104086777 B CN104086777 B CN 104086777B CN 201410310466 A CN201410310466 A CN 201410310466A CN 104086777 B CN104086777 B CN 104086777B
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Abstract
The invention relates to a preparation method of a PLA (poly lactic acid) modified material. The preparation method of the PLA modified material is characterized in that block polymerization is carried out on PLA resin and polyester by virtue of a double screw and flexible chain molecules are introduced in a preparation process. The preparation method of the PLA modified material has the advantages that a brand new formula is adopted, raw materials are modified, the size of a processing window is increased, free end groups are controlled, raw material stability is improved, performances of a film material are stable and a guarantee period of the film materials is at least three years; besides, by virtue of modification on the resin, softness, high tensile strength and other properties of a thin film hygienic material can be met.
Description
Technical field
The present invention relates to chemical field, the thin film that more particularly to a kind of disposable sanitary articles use, in particular it relates to
A kind of PLA is material modified and its manufacture method.
Background technology
At present, the thin film that disposable sanitary articles use is all polyethylene casting films.The thickness of polyethylene cast film is equal
Even, but because price is higher, be rarely employed at present, further according to existing formula system, there is poor fluidity, yield rate is low
Problem.
Polylactic acid (PLA) is a kind of new material, and the starch being proposed using reproducible plant resourceses (as Semen Maydiss) is former
Material is made, and because this material is taken from the biomaterials such as corn straw, product has antibacterial, ventilative characteristic, topmost
Feature is can to resolve into CO2 and water under conditions of compost.Reduce the white pollution of disposable health product or the expense of process
With.Therefore, its biodegradable performance is good.
So, polylactic acid (PLA), in addition to the basic characteristic having biodegradable plastic, is also equipped with the spy of oneself uniqueness
Property.The intensity of traditional biological degradation plastic, transparency and to the resistivity of climate change all not as plastics.Poly- breast
Sour (PLA) is similar with the basic physical properties of petrochemical industry synthetic plastic that is to say, that it can be widely used to make various applications products
Product.
Polylactic acid also has good glossiness and transparency, suitable with the thin film made using polystyrene, is other
Biodegradable product cannot provide.
Additionally, polylactic acid (PLA) has tensile strength the best and extensibility, polylactic acid can also various common process
Mode produces, for example：Fusing extrusion molding, ejection formation, blowfilm shaping, foaming and vacuum forming, with extensive institute at present
The polymer using has similar molding condition, and it also has and conventional films identical printing performance in addition.
But, often fragility is big for poly-lactic acid material, and soft, the high stretching that often cannot meet hygienic material thin film requirement is strong
The performances such as degree.
Content of the invention
It is contemplated that being directed to drawbacks described above, overcome current curtain coating polylactic acid film technique, the jejune problem of equipment, right
Its factory formula improves, and obtains a kind of product soft, that high tensile is good.
The present invention a kind of material modified manufacture method of PLA is provided it is characterised in that：By twin screw by PLA resin with
Polyester carries out block polymerization, introduces flexible molecules during manufacture.
Wherein, processing temperature is 170-200 DEG C, and extruder temperature is 170-200 DEG C, and T- mould is less than 210 DEG C (preferably
200 DEG C) it is ensured that resin melt temperature is less than 210 DEG C.
Chilled water temperature is 15-30 DEG C (preferably 15 DEG C), and cooling rubber roll and steel roll temperature control within 30 DEG C, set up
Tank spraying function, within its temperature is 30 DEG C, to guarantee material cooling and shaping with this, to keep soft and smooth appearance characteristics.
The present invention provide a kind of PLA material modified it is characterised in that, be fabricated by by the raw material of following mass fraction:
Wherein, polyester is selected from the compositionss of one or more of PET, PBT, PTT or copolyesters；
In the present invention, the main component of involved copolyesters is：
Main binary acid or dibasic ester composition be selected from the saturated fat dicarboxylic acids that carbon number is 2-18 and its derivant,
Carbon number is the unsaturated fatty acidss dicarboxylic acids of 2-18 and its aromatic dicarboxilic acid that derivant, carbon number are 2-18 and its derivative
Thing；
Main diol component is the saturated fat glycol of 2-18 for carbon number and its derivant, carbon number are 2-18
Unsaturated lipid aliphatic diol and its derivant, carbon number be the aromatic diol of 2-18 and its derivant；
Copolymer composition is selected from arbitrary dihydroxylic alcohols that carbon number is 2-18, dibasic ester or binary acid.
Preferably, polyester is Tritan copolyester, PETG, PCTA, PCTG, poly terephthalic acid-adipic acid-Isosorbide-5-Nitrae-fourth
The compositionss of one or more of diacid three-element copolymerized ester (PBTA).
Additionally, in the present invention, flexible molecules preferably are selected from polydimethylsiloxane, polyethers, polyethylene glycol oxide (molecular weight
200-20000, the compound being preferably more than 600 with molecular weight), cis-polybutadiene, polyethylene LLDPE, thermoplasticity third
Olefin(e) acid ester, trans- 1,4- polyisoprene etc. have the macromolecular compound of flexible chain.
Additionally, in the present invention, auxiliary agent is selected from carboxy blocking agent, antiblocking agent, chain extender, filler, softening agent, stablizes
The compositionss of one or more of agent, lubricant, plasticizer, surfactant, waterproofing agent.
Above-mentioned auxiliary agent preferably is selected from, carbodiimide compound, epoxide, isocyanate compound, paraffin, mineral oil,
Vegetable and animals oils, low molecule fluororesin, organic silicone oil, Low Density Polyethylene, stearic acid, stearate soap and its derivant, sour fat acid
Ester and its derivant, amide derivatives, oleamide, stearmide, the slaine of fatty acid, silicon dioxide, potter's clay, Linesless charcoal
Black, titanium dioxide, Calcium Carbonate, Isosorbide-5-Nitrae one butanediol, 1,6 one hexanediol, glycerol, trimethylolpropane, diethylene glycol, 2,2'-ethylenedioxybis(ethanol).,
Joncryl ADR-4368, neopentyl glycol, Sorbitol, diethylaminoethanol, MOCA, ethylenediamine, N, N- dihydroxy (diisopropyl
Base) aniline, hydroquinone one or two (β mono- ethoxy) ether, petroleum line softener, coal tar system softening agent, fatty oil softener, Oleum Pini
It is softening agent, lead salt stabilizer, Ba/Cd complex stabilizer, Ba/Zn complex stabilizer, Ca/Zn complex stabilizer, Ji Wusi
The mixture of one or more of alcohol, xylitol, Mannitol, epoxy soybean oil, epoxy fat.
In addition, in the present invention, the consumption of end-capping reagent is preferably 0.01-0.5 part；More preferably PLA and polyester gross mass
0.01-0.5%；
The consumption of lubricant is preferably 0.1-10 part；It is more preferably the 0.1-10% of PLA and polyester gross mass.
The consumption of antiblocking agent is preferably 0.1-1 part；It is more preferably the 0.1-1% of PLA and polyester gross mass.
The consumption of chain extender is preferably 0.01-5 part；It is more preferably the 0.01-5% of PLA and polyester gross mass.
The consumption of flexible molecules is preferably 0.1-10 part；It is more preferably the 0.1-10% of PLA and polyester gross mass.
The consumption of polyester is preferably 30-50 part；It is more preferably the 30-50% of PLA and polyester gross mass.
In addition, in the present invention, the thin film that the material modified purposes of above-mentioned PLA uses for disposable sanitary articles.
The effect of the present invention and effect
The present invention adopts brand-new formula, by the modification to raw material, increases process window and controls free end group,
Improve the stability of raw material, the performance of thin-film material can stably be guaranteed the quality at least 3 years；Additionally, can be full by this resin modified
The performances such as the softness of sufficient hygienic material thin film requirement, high tensile.
In the present invention, for the modification of raw material, it is mainly reflected in and by the PLA resin of different ratio and is gathered by twin screw
Ester carries out block polymerization, and in PLA material modified introducing flexible molecules, can improve the toughness of PLA well, reduces material crisp
Property, improve toughness and intensity.
In the present invention, mainly substitute the thin film of polyethylene with polylactic acid film, this film can be mainly used in sanitary towel, baby
Youngster's urine pants, the counterdie of adult diaper and peplos.
The advantage of polylactic acid film is:
(1), degrade：For disposal sanitary article (disposable product), the white pollution amount of generation is big, processing pressure
Greatly.And if doing peplos, counterdie using polylactic acid film, material 75% all of the above in health product adopts degradable material,
After then health product being used, concentrate and be deposited under certain composting conditionses, allow it all to degrade, reduce environmental pollution.
(2), breathability：Common polyethylene film has barrier, and polylactic acid film has breathability, can significantly carry
High sanitary towel or the comfortableness of urine pants.
(3), antibiotic property：Plain PE film needs to add auxiliary agent, gives thin film and has antibacterial effect.And polylactic acid is thin
Film, because properties of materials itself just has antibiotic property, is more suitably applied to hygienic material.
During as counterdie, its Main Function is antiseep, plays a protective role, some functional counterdies have antibacterial,
Ventilative effect.The thin film that peplos Ze Shi sanitary towel packaging uses, typically has white, printed patterns or colorful film.
And adopt inventive formulation technique manufacture counterdie product, its tensile strength, tearing strength, elongation percentage all compare
Height, can meet the processing request of the high-speed equipment of downstream client, meet the safety requirements of consumer's use simultaneously, will not produce
Seepage, the phenomenon such as tear.
The peplos being manufactured using the present invention, its outward appearance has certain deflection, and heat sealability is good it is ensured that downstream client sets
Seal intact during standby high-speed cruising, packaging is neat.Comfortable feel when consumer uses, sanitary towel package shape rule, totally
Beautiful.
Additionally, adding the raw materials such as titanium dioxide, Calcium Carbonate, stearic acid in the modifying process of the present invention, can also be used to carry
The characteristics such as the hiding rare of high material, surface smoothness.Add the trace assistants such as antioxidant, end-capping reagent, the heat of raw material can be improved
Stability and processing stability.
Specifically, in the present invention, selected carboxy blocking agent, its Main Function is to carry out the terminal carboxyl group of polylactic acid
Closing.Additionally, in the present invention this component can also by the carboxyl being generated by the decomposition reaction of polylactic acid or various additives,
The carboxyl closing of the low molecular compounds such as formic acid, makes stable resin, improves stablizing of curtain coating processing.
In the present invention, poly terephthalic acid-adipic acid -1, 4- succinic acid ternary polymerization that copolyester preferably employs
Ester, this is also a kind of material that can be degradable, and has the compliance of PBA segment and the thermostability of PBT segment and shock resistance concurrently
Property, therefore, PBTA and polylactic acid blend modification can be effectively improved the performance of polylactic acid.
In addition, being to improve its compatibility in the present invention, compatibilizing blending system can be come using chain extender, particularly preferably making
With：Joncryl ADR-4368, this compound due to its special product structure, for the raw material components such as, poly- breast of the present invention
Acid and PBTA etc. have the effect of good increase-volume.
By the modification of the present invention, properties of product improve 50-80% compared with conventional polyethylene casting films, stability；Toughness and
Intensity is respectively increased 30-50%, 20-45%.The hiding rare of material and surface smoothness also can have not according to product needed
With the raising of degree, generally 15-35%.
Specific embodiment
Embodiment one,
The material modified 1# of PLA, recipe ingredient：
PLAJoncryl ADR-4368 resin and polyester are carried out by block polymerization by twin screw, draws during manufacture
The components such as flexible molecules are entered.
Embodiment two,
The material modified 2# of PLA, recipe ingredient：
PLA resin and polyester are carried out by block polymerization by twin screw, during manufacture, introduces flexible molecules etc.
Component.
Embodiment three,
The material modified 3# of PLA, recipe ingredient：
PLA resin and polyester are carried out by block polymerization by twin screw, during manufacture, introduces flexible molecules etc.
Component.
Example IV,
The material modified 4# of PLA, recipe ingredient：
PLA resin and polyester are carried out by block polymerization by twin screw, during manufacture, introduces flexible molecules etc.
Component.
Embodiment five,
The material modified 5# of PLA, recipe ingredient：
PLA resin and polyester are carried out by block polymerization by twin screw, during manufacture, introduces flexible molecules etc.
Component.
Embodiment six,
The material modified 6# of PLA, recipe ingredient：
PLA resin and polyester are carried out by block polymerization by twin screw, during manufacture, introduces flexible molecules etc.
Component.
Embodiment seven,
The material modified 7# of PLA, recipe ingredient：
PLA resin and polyester are carried out by block polymerization by twin screw, during manufacture, introduces flexible molecules etc.
Component.
Embodiment eight,
The material modified 8# of PLA, recipe ingredient：
PLA resin and polyester are carried out by block polymerization by twin screw, during manufacture, introduces flexible molecules etc.
Component.
Embodiment nine,
The material modified 9# of PLA, recipe ingredient：
PLA resin and polyester are carried out by block polymerization by twin screw, during manufacture, introduces flexible molecules etc.
Component.
Embodiment ten,
The material modified 10# of PLA, recipe ingredient：
PLA resin and polyester are carried out by block polymerization by twin screw, during manufacture, introduces flexible molecules etc.
Component.
Claims (7)
1. a kind of PLA material modified it is characterised in that, be fabricated by by the raw material of following mass fraction:
Wherein, described flexible molecules be selected from polydimethylsiloxane, polyethers, thermoplastic propene's acid esters, polyethylene glycol oxide, along poly-
Butadiene, polyethylene LLDPE, trans- 1,4- polyisoprene；
Described auxiliary agent is selected from carboxy blocking agent and antiblocking agent, lubricant, chain extender, filler, softening agent, stabilizer, surface work
The compositionss of one or more of property agent, waterproofing agent；
Its manufacture method is as follows：PLA resin and polyester are carried out by block polymerization by dual-screw-stem machine, draws during manufacture
Flexible molecules are entered, wherein, the processing temperature of dual-screw-stem machine is 170-200 DEG C, and extrusion temperature is 170-200 DEG C, and T- mould is low
In 210 DEG C.
2. as claimed in claim 1 a kind of PLA material modified it is characterised in that：Described polyester is selected from PET, PBT, PTT or common
The compositionss of one or more of polyester；
Wherein, the main component of described copolyesters is：
Main binary acid or dibasic ester composition are selected from the saturated fat dicarboxylic acids that carbon number is 2-18 and its derivant, carbon are former
Subnumber is the unsaturated fatty acidss dicarboxylic acids of 2-18 and its aromatic dicarboxilic acid that derivant, carbon number are 2-18 and its derivant；
Main diol component be the saturated fat glycol of 2-18 for carbon number and its derivant, carbon number be 2-18 not
Saturated fat glycol and its derivant, carbon number are aromatic diol and its derivant of 2-18；
Copolymer composition is selected from arbitrary dihydroxylic alcohols that carbon number is 2-18, dibasic ester or binary acid.
3. as claimed in claim 1 a kind of PLA material modified it is characterised in that：Described polyester be selected from Tritan copolyester,
PETG, PCTA, PCTG, poly terephthalic acid-adipic acid -1, 4- succinic acid three-element copolymerized ester.
4. as claimed in claim 1 a kind of PLA material modified it is characterised in that：Described auxiliary agent is selected from carbodiimide chemical combination
Thing, epoxide, isocyanate compound, paraffin, mineral oil, vegetable and animals oils, low molecule fluororesin, organic silicone oil, low close
Degree polyethylene, stearic acid, stearate soap and its derivant, acid fatty acid ester and its derivant, oleamide, stearmide, fat
Acid slaine, silicon dioxide, potter's clay, white carbon, titanium dioxide, Calcium Carbonate, Isosorbide-5-Nitrae one butanediol, 1,6 one hexanediol, glycerol, three
Hydroxymethyl-propane, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., Joncryl ADR-4368, neopentyl glycol, Sorbitol, diethylaminoethanol, MOCA,
Ethylenediamine, N, N- dihydroxy (diisopropyl) aniline, hydroquinone one or two (β mono- ethoxy) ether, petroleum line softener, coal tar system are soft
Agent, fatty oil softener, pine tar softener, lead salt stabilizer, Ba/Cd complex stabilizer, Ba/Zn stable composition
One or more of agent, Ca/Zn complex stabilizer, tetramethylolmethane, xylitol, Mannitol, epoxy soybean oil, epoxy fat mixed
Compound.
5. as claimed in claim 1 a kind of PLA material modified it is characterised in that：
The consumption of described carboxy blocking agent is 0.01-0.5 part；
The consumption of described lubricant is 0.1-10 part；
The consumption of described antiblocking agent is 0.1-1 part；
The consumption of described chain extender is 0.01-5 part；
The consumption of described flexible molecules is 0.1-10 part.
6. as claimed in claim 1 a kind of PLA material modified it is characterised in that：
The consumption of described carboxy blocking agent is the 0.01-0.5% of PLA and polyester gross mass；
The consumption of described lubricant is the 0.1-10% of PLA and polyester gross mass；
The consumption of described antiblocking agent is the 0.1-1% of PLA and polyester gross mass；
The consumption of described chain extender is the 0.01-5% of PLA and polyester gross mass；
The consumption of described flexible molecules is the 0.1-10% of PLA and polyester gross mass；
The consumption of described polyester is the 30-50% of PLA and polyester gross mass.
7. described a kind of PLA as arbitrary in claim 1-6 material modified it is characterised in that：The material modified purposes of described PLA
The thin film using for disposable sanitary articles.
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| CN105200380A (en) * | 2015-07-30 | 2015-12-30 | 宁波华丰包装有限公司 | Magnetron sputtering high barrier film and production technology thereof |
| CN106987107A (en) * | 2017-05-18 | 2017-07-28 | 中国科学院长春应用化学研究所 | A kind of degradable resin composition and degradable resin film |
| CN110423442A (en) * | 2019-08-12 | 2019-11-08 | 宜兴西工维新科技有限公司 | A kind of degradable composite membrane and preparation method thereof |
| CN111662596B (en) * | 2020-06-04 | 2022-08-05 | 广东康烯科技有限公司 | Preparation method of PTC graphene-based conductive ink and PTC graphene-based conductive ink |
| CN111560190A (en) * | 2020-06-05 | 2020-08-21 | 广东康烯科技有限公司 | Preparation method of PTC graphene-based conductive ink and PTC graphene-based conductive ink |
| CN112375237B (en) * | 2020-10-06 | 2022-01-11 | 江苏双星彩塑新材料股份有限公司 | Functional master batch production system for polyester film |
| CN112920412B (en) * | 2021-04-15 | 2022-12-27 | 上海朗亿功能材料有限公司 | Polycarbodiimide-containing polylactic resin and preparation method thereof |
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Effective date of registration: 20210713 Address after: 201108 Building 9, 1288 zhuanxing Road, Minhang District, Shanghai Patentee after: Shanghai Zihua Film Technology Co.,Ltd. Address before: 201111 No. 999 North Song Road, Shanghai, Minhang District Patentee before: SHANGHAI ZIHUA ENTERPRISE Co.,Ltd. |