CN105419264A - Flame-retardant polylactic resin composition - Google Patents
Flame-retardant polylactic resin composition Download PDFInfo
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- CN105419264A CN105419264A CN201510458008.7A CN201510458008A CN105419264A CN 105419264 A CN105419264 A CN 105419264A CN 201510458008 A CN201510458008 A CN 201510458008A CN 105419264 A CN105419264 A CN 105419264A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The present invention relates to a flame-retardant polylactic resin composition, characterized by containing: (A) 85%-95% by weight of polylactic resin; (B) 3%-10% by weight of phosphorus-based flame retardant; and (C) 2%-5% by weight of nitrogen-based flame retardant. The flame-retardant polylactic resin composition is characterized in that smoke production quantity during combustion is greatly reduced, and the flame-retardant polylactic resin composition is suitable for internal and external materials of electrical and electronic components, shells and so on.
Description
Technical field
The present invention relates to a kind of flame retardant polylactic acid resin combination of the cigarette generation produced when greatly reducing burning.
Background technology
Be not only that the petroliferous fossil fuel resource of bag can be at a time exhausted, and in the process using it, produce the carbonic acid gas causing greenhouse effects of the earth.Therefore, the polymer starting material of the oil fuel obtained by petroleum resources and petroleum chemistry base are replacing with biomass-based starting material.Poly(lactic acid) (polylacticacid in this biomass-based starting material, PLA) be raw material with plants starch and for receiving much concern in neutral carbon (carbonneutral), as the resin from oil equivalent material and be expected to.Poly(lactic acid), due to Biodegradable characteristic, is therefore used to disposable product etc., but in order to be applicable to electronic device field and automobile part etc., additionally needing flame retardant resistance, when burned, also must consider cigarette generation.In fact, when producing fire, also there is the situation of death because fire is not extinguished, but report and cause larger impact as the cigarette of by product of burning and poisonous gas.
In Korean Patent KR10-1038466, after fire retardant and polyester are carried out copolymerization and manufacture flame retardant resistance aliphatic polyester resin, manufactured flame-retardant polyester resin and polylactic resin are carried out mixing with certain ratio and give flame retardant resistance to acid fiber by polylactic.But also may there is the situation that the intermiscibility of poly(lactic acid) and flame-retardant polyester resin is low, flame retardant resistance evaluation only have rated LOI (limiting oxygen index(LOI), LimitedOxygenIndex), can not learn flame retardant effect exactly.
In KR published patent KR10-2011-0032183, propose the flame retardant polylactic acid resin combination containing flame-retardant polyester resin, but similarly, flame retardant resistance evaluation only have rated LOI, can not learn flame retardant effect exactly.
In Japanese Patent JP5273646B9, propose the flame retardant polylactic acid divided containing phosphorus flame retardant and antidrip completion, but flame retardant resistance evaluation only carries out UL94.
In Japanese Patent JP5378904B9, to propose except poly(lactic acid) the polylactic acid resin composition also containing thermoplastic resin, phosphorus system or nitrogen system or metal oxide flame retardant and flame retardant, but flame retardant resistance only have rated UL94.
Summary of the invention
Invent problem to be solved
The present invention for providing a kind of flame retardant polylactic acid resin combination to environment gentleness greatly reducing cigarette generation, with usefully for the existing such molding manufacture such as interior exterior material, shell (ケ ー ス) class being suitable for the flame retardance poly ethylene glycol terephthalate (PET) of petroleum chemistry base, the electrical/electronic part of flame-retardant polybutylene terephthalate (PBT).
For solving the scheme of problem
In order to solve described problem, the invention provides a kind of flame retardant polylactic acid resin combination, it contains: (A) polylactic resin 85 ~ 95 % by weight, (B) phosphorus flame retardant 3 ~ 10 % by weight and (C) nitrogen system flame retardant 2 ~ 5 % by weight.
Invention effect
Flame retardant polylactic acid resin combination of the present invention has the feature greatly reducing cigarette generation, and flame retardant resistance is also very excellent simultaneously, therefore, goes for the interior exterior material of electrical/electronic part, shell class etc.
In environment, when the plastics of petroleum replacing chemical based, there is the effect that can reduce carbonic acid gas as the raw-material poly(lactic acid) to environment gentleness by containing.
Embodiment
The feature of flame retardant polylactic acid resin combination of the present invention is, contains: (A) polylactic resin 85 ~ 95 % by weight, (B) phosphorus flame retardant 3 ~ 10 % by weight and (C) nitrogen system flame retardant 2 ~ 5 % by weight.
Below, each composition contained in the flame retardant polylactic acid resin combination of a specific example of the present invention is described in further detail.
(A) polylactic resin (polylacticacid, PLA)
Poly(lactic acid) is typical aliphatic polyester based resin, for using the Biodegradable polymer of the monomer synthesize obtained by 100% reproducible resources such as the starch of corn and potato.
Described poly(lactic acid) is manufactured by the polymerization of the lactic acid (lacticacid) as monomer.Lactic acid can utilize the fermentation method of method and the cereal resource of chemically synthesizing to produce.The lactic acid chemically synthesized by fossil feedstock is by being mixed with L-type and each racemic mixture of 50 % by weight of D-type lactic acid makes, on the other hand, utilizing in amylaceous fermented method, the L-type lactic acid of more than 99.5 % by weight can be obtained, therefore, the production method of the fermentation of food resource is preferably utilized.At present, lactic acid uses the glucose that obtained by the most cheap, the abundantest W-Gum and manufactures.
In the present invention, as described polylactic resin, Poly-L-lactide, poly-D-ALPHA-Hydroxypropionic acid, poly-(D, L)-lactic acid or their combination can be used.Described poly(lactic acid) preferably uses the poly(lactic acid) that the optical purity of lactic acid is high.Optical purity is higher, thermotolerance and crystallization rate faster, therefore, preferred optical purity is the poly(lactic acid) of more than 95%.
As long as the molecular weight of the poly(lactic acid) used in the present invention can carry out injection forming, then molecular weight, molecular weight distribution are not particularly limited, preferable weight-average molecular weight is 50,000 ~ 400,000g/mol, in order to improve the physical strength of molding further, further preferably 100,000 ~ 400,000g/mol.
In flame retardant polylactic acid resin combination of the present invention, the content of described poly(lactic acid) is preferably 85 ~ 95 % by weight with the weight basis of all resin combinations.When containing described polylactic resin with above-mentioned scope, the polylactic acid resin composition of the balancing good of processibility and mechanical properties can be guaranteed.
(B) phosphorus flame retardant
Generally speaking; phosphorus flame retardant generates phosphoric acid, metaphosphoric acid, poly-metaphosphoric acid by thermolysis, by playing flame retardant resistance by the blocking effect utilizing the charing (char) being formed and utilize the dehydration of poly-metaphosphoric acid to generate of the protective layer of phosphoric acid layer to cause.
Fire retardant can divide into addition type and reactive flame retardant according to the method for giving flame retardant resistance.Additive flame retardant is put into as additive and mixes simply in cooperation (compounding) operation, reactive flame retardant imports and can give the monomer of flame retardant resistance and manufacture retardant polymer compound on the main chain of macromolecular compound, or in macromolecular compound, import reactive group, chemically bonding flame retardant resistance material and give flame retardant resistance on the end or side chain of macromolecular compound.
In the present invention, as phosphorus flame retardant, both addition type and response type all can use.As described addition type phosphorus flame retardant, there are phosphoric acid ester or phosphoric acid ester (phosphate), as the example, two (phenylbenzene) phosphoric acid ester (resorcinolbis (diphenylphosphate), RDP) of Resorcinol is representational.As described reactive phosphorus flame retardant, the compound shown in following chemical formula 1 can be used.In following chemical formula 1, R
1for virtue (aryl) base of phenyl (phenyl), benzyl (benzyl), tolyl (tolyl), xylyl (xylyl) and so on, R
2for the alkyl of carbon number 1 ~ 10.Representational described reactive phosphorus flame retardant is 3-(hydroxyphenylphosphinyl) propionic acid.
[chemical formula 1]
In flame retardant polylactic acid resin combination of the present invention, the content of described phosphorus flame retardant is preferably 3 ~ 10 % by weight with the weight basis of all resin combinations.The content of described phosphorus flame retardant lower than 3 % by weight time, the weak effect of fire retardant, when it is more than 10 % by weight, is effective in flame retardant resistance, but cigarette generation less reduces, mechanical properties reduces, economy aspect is not preferred yet.
(C) nitrogen system flame retardant
Generally speaking, flame retardant is in order to make the content of fire retardant reduce and make flame retardant resistance maximize and use.Nitrogen system flame retardant is produce and the synergy of phosphorus flame retardant, material that flame retardant resistance is improved.As described nitrogen system flame retardant, more than a kind in compound nitrogen series such as being selected from trimeric cyanamide, three (hydroxyethyl) isocyanuric acid ester (THEIC), melamine phosphate (MP), melamine polyphosphate (MPP), melamine cyanurate (MC) can be enumerated.
In flame retardant polylactic acid resin combination of the present invention, the content of described nitrogen system flame retardant is preferably 2 ~ 5 % by weight with the weight basis of all resin combinations.The content of described nitrogen system flame retardant lower than 2 % by weight time, poor with the synergy of fire retardant, when it is more than 5 % by weight, the mechanical properties of polylactic acid resin composition is poor, therefore not preferred.
Additionally, composition of the present invention can contain mineral filler further in order to improve mechanical properties.Mineral filler representatively, has glass fibre, the mineral filler that glass fibre is thermotolerance in order to make polylactic acid resin composition, the mechanical properties of tensile strength and bending elastic modulus and so on improves and adds.Particularly preferably described glass fibre is shortly cut (chop) form, the glass fibre of chopped strand (choppedstrands) form that more specifically, preferred diameter is 10 ~ 15 μm, length is 3 ~ 5mm.
Described glass fibre when fiber manufactures or postprocessing working procedures time finishing agent for glass fibre (sizingcompositions) can be utilized to process, as described finishing agent for glass fibre, have lubricant, coupling agent etc.Described profit lubricant uses mainly for forming good precursor (strand) when glass fibre manufactures.Described coupling agent for improving the bonding force between glass fibre and polylactic resin, when consider the kind of polylactic resin and glass fibre and suitably choice for use, excellent physical property can be given to described polylactic acid resin composition.As described coupling agent, preferably use the silane system material with organo-functional groups such as vinyl, epoxy group(ing), thiol group, amidos.
In addition, additionally, composition of the present invention also can according to required characteristic further containing additive.As described additive, it can be more than a kind in thermo-stabilizer, antioxidant, photostabilizer, releasing agent, dyestuff, pigment, tinting material, nucleator, softening agent, impact stiffeners, hydrolysis preventing agent, stablizer and lubricant.
The present invention more specifically can be understood by following embodiment, and following embodiment only for illustrating example of the present invention, does not limit the scope of the invention.
Each constituent of the flame-proof polylactic acid resin combination used in embodiments of the invention and comparative example is as described below.
(A) poly(lactic acid)
Use the 4032D manufactured by ネ イ チ ャ ー ワ ー Network ス (NatureWorksLLC) society of the U.S..
(B-1) addition type phosphorus flame retardant
Use the ReofosRDP (two (phenylbenzene) phosphoric acid ester of Resorcinol) manufactured by U.S. ケ system チ ュ ラ (Chemtura) society.
(B-2) reactive phosphorus flame retardant
Use by the KOLON (コ ー ロ Application of Korea S) Hiretar205 as reactive phosphorus flame retardant ((3-hydroxyphenylphosphinyl (Port Le Off ィ ニ Le)) propionic acid) that manufactures of life science.
(C) nitrogen system flame retardant
Use the trimeric cyanamide manufactured by pure (Junsei) society of Japan.
(D) polyethylene terephthalate (PET)
Use the SKY-PETBR manufactured by the SKchemicals society of Korea S.
(E) polybutylene terephthalate (PBT)
Use the KP211 manufactured by Korea S KOLON plastics.
Embodiment 1 ~ 2 and comparative example 1 ~ 9
With the content shown in following table 1, each constituent is carried out mixing and after manufacturing resin combination, twin screw extruder (bis-Shaft Ya Chu Machine with L/D40, diameter 30mm) extrude in the temperature range of 160 ~ 230 DEG C after, extrudate is manufactured particle form.In following table 1, the content unit of each constituent is % by weight.At 80 DEG C, after dry 4 hours, automatic press is used to make fire-retardant evaluation test film the particle manufactured by method as above.The following method of described fire-retardant evaluation measures, and the results are shown in following table 2.
Fire-retardant evaluation
1) flame retardant resistance: based on UL94, evaluates flame retardant resistance with the test film of 3mm thickness.
2) total heat discharging amount (THR, TotalHeatRelease): based on ISO5660, uses conecalorimeter (FESTEC society) equipment to evaluate.
3) total cigarette generation (TSP, TotalSmokeProduction): based on ISO5660, uses conecalorimeter (FESTEC society) equipment to evaluate.
ISSO5660 (Reaction-to-firetests:Heatrelease, smokeproductionandmasslossrate) specifies evaluating the test method being exposed to the dynamic cigarette production rate of photothermal flattening test body.This test method generally based on the intensity of the light through combustion products according to distance with this situation of long-pending minimizing (Bouguer rule) of exponential function.For the test body tested while accept predetermined 0 ~ 100kW/m
2external radiation heat in scope, makes it burn in atmospheric conditions and measures the rate of mass reduction of delustring, exhaust gas flow and test body.Delustring with via be positioned at exhaust-duct cigarette and through the ratio of intensity of light measure.This ratio according to Bouguer rule, for calculating reduction coefficient.Test-results represents has carried out standardized total cigarette generation and cigarette production rate by the surface-area of the test body exposed.Cigarette production rate calculates by reduction coefficient with by the product of the suitableeest flow of the cigarette in exhaust-duct.Total cigarette generation is divided by the integration (Lei Plot considered in the time-bands of cigarette production rate) obtain.Described total cigarette generation and cigarette production rate can be calculated by following formula.
S=P
sintegration
P
s＝k×V
s
k＝ln(l
0/l)/L
V
s＝m
e×T
s/(12.2×10
3×M)
S: total cigarette generation [m
2]
P
s: cigarette production rate [m
2/ s]
K: reduction coefficient [m
-1]
Ln: natural logarithm
L
0: the intensity [W/m of light when not having a cigarette
2]
L: the intensity [W/m of the light of minimizing
2]
L: by the path [m] of the light of cigarette
V
s: the volumetric flow rate [m measuring the cigarette at fulcrum place
3/ s]
M
e: the mass rate [kg/s] measured with orifice plate (orifice)
T
s: the cigarette temperature [K] measuring fulcrum place
M: the molecular weight of flowing air by exhaust-duct, 0.029 [kg/mol]
Table 1
(unit: % by weight)
Table 2
From the result of the embodiment shown in described table 1 and table 2 and comparative example, can confirm: there is the flame retardant polylactic acid resin combination of the embodiment 1 ~ 2 of composition of the present invention compared with employing the comparative example 1 of 100 % by weight poly(lactic acid), not only cigarette generation greatly reduces, and flame retardant resistance is also excellent.That is, known: embodiment 1 and embodiment 2, by the phosphorus flame retardant that uses in the present invention and flame retardant, achieve V-0 flame retardant resistance and total cigarette generation can greatly reduce.
From employ poly(lactic acid) 100 % by weight comparative example 1, employ the comparative example 6 of polyethylene terephthalate 100 % by weight and employ the result of comparative example 8 of polybutylene terephthalate 100 % by weight: all burn when there is no fire retardant, simultaneously total heat discharging amount and cigarette generation high.
Result from comparative example 2: all burn when the content of addition type phosphorus flame retardant is 1 % by weight.
Result from comparative example 3: when the content of reactive phosphorus flame retardant is 2 % by weight, V-2 flame retardant resistance can be realized, but total cigarette generation does not greatly reduce.
Result from comparative example 4 and comparative example 5: when the content of addition type phosphorus flame retardant and reactive phosphorus flame retardant is respectively 20 % by weight, V-1, V-0 flame retardant resistance can be realized, but total cigarette generation does not greatly reduce.
Comparative example 7 and comparative example 9 are respectively the situation employing fire retardant polyethylene terephthalate, fire retardant polybutylene terephthalate, and the reduction effect of known total cigarette generation is little.
By result as above in general, flame retardant polylactic acid resin combination of the present invention has the feature that cigarette generation greatly reduces, flame retardant resistance is also very excellent simultaneously, therefore, can usefully for the molding manufacture of the interior exterior material, shell class etc. that are suitable for the electrical/electronic part of fire retardant polyethylene terephthalate (PET) and fire retardant polybutylene terephthalate (PBT) and so on.
Claims (9)
1. a flame retardant polylactic acid resin combination, it contains
(A) polylactic resin 85 ~ 95 % by weight;
(B) phosphorus flame retardant 3 ~ 10 % by weight; And
(C) nitrogen system flame retardant 2 ~ 5 % by weight;
Flame retardant rating is total cigarette generation of V-0,3mm Thickness Test sheet benchmark is 2.0m
2below.
2. flame retardant polylactic acid resin combination according to claim 1, is characterized in that,
Described poly(lactic acid) is Poly-L-lactide, poly-D-ALPHA-Hydroxypropionic acid, poly-(D, L)-lactic acid or their combination, and optical purity is more than 95%, and weight-average molecular weight is 50,000 ~ 400,000g/mol.
3. flame retardant polylactic acid resin combination according to claim 1, is characterized in that,
Described phosphorus flame retardant is the reactive phosphorus flame retardant shown in two (phenylbenzene) phosphoric acid ester of Resorcinol or following chemical formula:
At this, R
1for phenyl, benzyl, tolyl or xylyl,
R
2for the alkyl of carbon number 1 ~ 10.
4. flame retardant polylactic acid resin combination according to claim 3, is characterized in that,
Described reactive phosphorus flame retardant is 3-(hydroxy phenyl phosphono) propionic acid.
5. flame retardant polylactic acid resin combination according to claim 1, is characterized in that,
Described nitrogen system flame retardant is for being selected from more than a kind in trimeric cyanamide, three (hydroxyethyl) isocyanuric acid ester, melamine phosphate, melamine polyphosphate and melamine cyanurate.
6. flame retardant polylactic acid resin combination according to claim 1, is characterized in that, described composition is also containing glass fibre.
7. flame retardant polylactic acid resin combination according to claim 6, is characterized in that, the chopped strand form that described glass fibre is diameter is 10 ~ 15 μm, length is 3 ~ 5mm.
8. flame retardant polylactic acid resin combination according to claim 6, is characterized in that, the described glass fibre silane system material with the organo-functional group be selected from vinyl, epoxy group(ing), thiol group, amido processes.
9. the interior exterior material of electrical/electronic part or a shell class injection-molded article, wherein, containing the flame retardant polylactic acid resin combination according to any one of claim 1 ~ 8.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140121102A KR20160031609A (en) | 2014-09-12 | 2014-09-12 | Flame-retardant polylactic acid composition |
| KR10-2014-0121102 | 2014-09-12 |
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|---|---|
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| CN105419264B CN105419264B (en) | 2018-06-29 |
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Cited By (2)
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| CN106243656A (en) * | 2016-09-29 | 2016-12-21 | 青岛海之源智能技术有限公司 | A kind of anti-flaming environment-friendly polylactic acid plastic and preparation method thereof |
| CN111363322A (en) * | 2018-12-26 | 2020-07-03 | 浙江海正生物材料股份有限公司 | Flame-retardant polylactic resin composition and preparation method thereof |
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| CN113462002B (en) * | 2021-06-29 | 2023-03-31 | 北京化工大学常州先进材料研究院 | Preparation method of degradable flame-retardant foamed beads |
| CN115637032B (en) * | 2021-07-20 | 2024-06-11 | 北京服装学院 | Heat-resistant flame-retardant polylactic acid material and preparation method thereof |
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Also Published As
| Publication number | Publication date |
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| CN105419264B (en) | 2018-06-29 |
| KR20160031609A (en) | 2016-03-23 |
| JP6050443B2 (en) | 2016-12-21 |
| JP2016060908A (en) | 2016-04-25 |
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