CN1922269A - Copolymer-containing aliphatic polyester resin composition - Google Patents

Abstract

The invention provides a resin composition containing an aliphatic polyester resin having an excellent heat resistance and impact resistance and automobile materials, home electric appliance material parts, and electric and electronic parts produced from said resin composition. [Means for solving problems] Production of a specific resin composition (D) having an excellent heat resistance and impact resistance, containing an aliphatic polyester resin (A), a polyolefin resin (B) and a modified polyolefin resin (C) and molding of automobile materials, home electric appliance material parts, and electric and electronic parts using said resin composition.

Description

The aliphatic polyester resin composition that contains multipolymer

Technical field

The present invention relates to a kind of resin combination (D), it is characterized in that containing aliphatic polyester resin (A), polyolefin resin (B) and modified polyolefin resin (C), and a kind of resin formed article with excellent heat resistance and shock-resistance that obtains from resin combination (D).

Background technology

As everyone knows, the global environment problem constantly increases, because fossil feedstock (fossil material) and the exhaustion of petroleum resources and the increase of carbonic acid gas become problem, the use plant as the biodegradable resin of raw material for example the research and development of aliphatic polyester and resin enliven.In aliphatic polyester, the excellent especially poly(lactic acid) of plasticity-is as a kind ofly deriving from plant, using the resin that is obtained by the lactic acid of cereal source as corn fermentation acquisition to cause attention.But poly(lactic acid) is except that its hard, crisp defective, and its crystallization rate is low, and therefore poor heat resistance has limited its Application Expansion.Particularly, for example, under the amorphous molded situation of poly(lactic acid) because softening temperature is lower than 60 ℃, can appear under the daily environment for use bleach easily, the problem of distortion and similar variation.And, thereby the lactyl resin need improve these character of lactyl resin because its inflexible molecular structure has the poor very crisp defective of shock strength.

Traditionally, the technology that is known as polymer blend or polymer alloy is arranged, it is known to be the method for improving the resin physical properties.Various kinds of resin mixed by force and mediate (knead), attempt shock-resistance, elasticity, rigidity and thermotolerance are improved.By different resins is mixed with aliphatic polyester, some trials of physical properties have been carried out improving.For example, JP-A-10-251498 discloses by 1 to 15wt.% syndiotactic polypropylene is mixed the polylactic acid based resin combination that the shock-resistance that obtains is improved with poly(lactic acid).In addition, JP-A-9-316310 discloses by the modified olefin compound is mixed the method for improving the poly(lactic acid) shock-resistance with poly(lactic acid).In addition, JP-A-2002-37987 discloses by poly(lactic acid) is mixed obtain a kind of with thermoplastic elastomer (ethylene-propylene-elastoprene) and has fused the poly (lactic acid) composition that characteristic, mechanical characteristics and shock-resistance are improved.

But to improve stable on heating method then rarely known by the people by different resins is mixed with poly(lactic acid).Particularly, improve stable on heating trial and do not know as yet by mixing with poly(lactic acid) such as the fast polypropylene of crystallization rate.Above-mentioned JP-A-10-251498 has described mixed polypropylene, and to have used the small amount of crystalline degree be 40% or lower low crystallization syndiotactic polypropylene.Refuse to take a passenger, when using degree of crystallinity as the common high-crystallinity polypropylene of 60-70%, the blending dispersion state is very poor, and not preferred.In addition, refuse to take a passenger, the consumption of syndiotactic polypropylene is limited in 15wt.% or lower, when surpassing 15wt.%, just can not obtain uniform composition.When only having a small amount of 15wt.% or low crystallization syndiotactic polypropylene still less to mix, can not realize enough thermotolerances with poly(lactic acid).Consistency between polyolefin resin and the polylactic acid based resin is extremely low, only by with its mixing with mediate and then can be separated or incompatible, is difficult to the physical properties (particularly thermotolerance) that obtains to expect.

On the other hand, as the method for improving the aliphatic polyester resin shock-resistance, for example, JP-A-10-251498 discloses the method that adds modified olefin in poly(lactic acid).JP-A-11-124495 then discloses the method for the multipolymer that adds other flexible aliphatic polyester and poly(lactic acid).In addition, non-patent literature 1 (MACROMOLECULAR CHEMICAL andPHYSICS, 1996, the 197 volumes, 1503-1523 page or leaf) discloses the method that adds poly-(6-caprolactone) (it is a kind of aliphatic polyester).But the improvement of these method impact intensity needs to add a large amount of properties-correcting agent and improves shock strength not enough.This has just produced plasticity-or the ruined problem of thermotolerance.

Incidentally, as the method for improving the resin shock strength, the method that flexible rubber is dispersed in the resin is known.Known when the particle diameter that be dispersed in the rubber in the resin be about a few μ m or more hour, can improve shock strength effectively like this.But two kinds of polymkeric substance are compatible with each other very difficult usually, and therefore, the rubber size that joins in the resin becomes very big, and shock strength can't be improved.Add the expanding material that improves consistency between two kinds of polymkeric substance and can greatly improve the dispersion state of rubber, thereby reduce the interfacial tension between the different polymkeric substance.

Compound with polymkeric substance of two kinds of compatible blocks respectively is regarded as having the effect that excellent conduct improves the expanding material of rubber dispersion state, according to non-patent literature 2 (JOURNAL OFAPPLIED POLYMER SCIENCE, 2003, the 89th volume, the 3757-3768 page or leaf) described, can greatly improve the shock strength of poly(lactic acid) by in the mixture of poly(lactic acid) and linear low density polyethylene, adding poly(lactic acid) and poly block polymer.But shortcoming is that poly(lactic acid) and poly block polymer relate to complicated polymerization process, are easy to increase cost like this.

In addition, treat the rubber of fine dispersion and the consistency between the resin, rubber can be dispersed in the resin subtly by improvement.A kind of method of improving rubber and interlaminar resin consistency is to join in the rubber with the good position of resin compatible.For example, according to non-patent literature (PolymerABC Handbooks, Polymer Society, Polymer ABC Research chief editor, publish January 1 calendar year 2001, the 372-379 page or leaf) described, in rubber-reinforced polystyrene (HIPS),, styrene-grafted improves shock strength in the styrene resin on rubber and with it by being dispersed in.But different with ethene polymers such as styrene resin, in ester polycondensate such as polylactic resin, it is very difficult to make segmented copolymer, graft copolymer or random copolymers with the rubber that effectively improves shock strength.

Summary of the invention

The problem that the present invention solves

The problem that the present invention solves is to obtain a kind of resin combination (D), its have by improve between aliphatic polyester resin (A) and the polyolefin resin (B) consistency and with island phase (island phase) fine dispersion in resin combination and improved thermotolerance and shock-resistance.The method of dealing with problems

The present inventor has been found that, the resin combination (D) that contains aliphatic polyester resin (A), polyolefin resin (B) and modified polyolefin resin (C), and the thermotolerance that is obtained by resin combination (D) and the moulded product of shock-resistance excellence possess excellent characteristic, can address the above problem, realize purpose of the present invention.

The present invention specifies and is listed below.

(1) a kind of resin combination (D) is characterized in that containing the aliphatic polyester resin (A) of 1 to 99 weight part and the polyolefin resin (B) of 99 to 1 weight parts (condition is 100 weight parts for (A) and summation (B)) and is the modified polyolefin resin (C) of 0.1 to 100 weight part of 100 weight parts based on (A) and summation (B).

(2) resin combination (D), it is characterized in that described modified polyolefin resin (C) contain being selected from of 0.1 to 100 weight part (C-1), (C-2) and (C-3) at least a;

(C-1) has the multipolymer of following structure: propenyl polyolefine segment, (a) and contain the segment of lactic acid as integral part, (b) by covalent linkage with block state and/or the combination of grafting shape, propenyl polyolefine segment wherein, (b) number-average molecular weight is 1,000 to 100,000, contain the segment of lactic acid as integral part, (a) number-average molecular weight is 1,000 to 200,000, propenyl polyolefine segment, (a) and contain the segment of lactic acid as integral part, (b) weight consists of from 10/90 to 90/10

(C-2) have the multipolymer of following structure: contain the acrylic acid series unit as the segment of integral part and vinyl (ethylene-based) polyolefine segment by covalent linkage with block state and/or grafting state and/or disorganized form combination and

(C-3) have the multipolymer of following structure: contain the acrylic acid series unit as the segment of integral part and propenyl (propylene-based) polyolefine segment by covalent linkage with block state and/or grafting state and/or disorganized form combination.

(3) a kind of modified polyolefin resin (C-1), it comprises the multipolymer with following structure: propenyl polyolefine segment (a) and contain lactic acid as the segment (b) of integral part by covalent linkage with block state and/or grafting combinations of states, wherein the number-average molecular weight of propenyl polyolefine segment (b) is 1,000 to 100,000, containing lactic acid is 1 as the number-average molecular weight of the segment (a) of integral part, 000 to 200,000, propenyl polyolefine segment (a) and contain lactic acid and consist of 10/90 to 90/10 as the weight of the end of the chain (b) of integral part.

(4) according to the manufacture method of the modified polyolefin resin (C-1) of above-mentioned (1) to (3), it is characterized in that to contain monomer and polyolefin resin polymerization in the presence of modified polyolefin resin of rac-Lactide or lactic acid, wherein said modified polyolefin resin has the grafting vinyl monomer that contains hydroxyl thereon, perhaps vinyl monomer and polymer of monomers that contains rac-Lactide or lactic acid and polyolefine reaction.

(5) according to the resin combination (D) of above-mentioned (1) and (2), wherein said modified polyolefin resin (C-2) is to have to contain acrylic acid units as the segment of integral part and the multipolymer of vinyl polyolefin block.

(6) according to the resin combination (D) of above-mentioned (1) and (2), wherein said modified polyolefin resin (C-2) is to have to contain methyl methacrylate units as the segment of integral part and the multipolymer of vinyl polyolefin block.

(7) according to the resin combination (D) of above-mentioned (1) and (2), wherein said modified polyolefin resin (C-3) is to have to contain acrylic acid units as the segment of integral part and the multipolymer of propenyl polyolefin block.

(8) according to the resin combination (D) of above-mentioned (1) and (2), wherein said modified polyolefin resin (C-3) is to have to contain methyl methacrylate units as the segment of integral part and the multipolymer of propenyl polyolefin block.

(9) a kind of resin combination (D), it is characterized in that it is obtained by the resin combination that contains following component: the polyolefin resin (B) of the aliphatic polyester resin of 40 to 99 weight parts (A), 60 to 1 weight parts (condition is 100 weight parts for (A) and summation (B)), as modified polyolefin resin (C) based on (A) and summation (B) be being selected from of 0.1 to 50 weight part (C-1), (C-2) of 100 weight parts and (C-3) at least a, and its softening temperature is 60 ℃ or higher.

(10) a kind of resin combination (D), it is characterized in that it is obtained by the resin combination that contains following component: the polyolefin resin (B) of the aliphatic polyester resin of 40 to 99 weight parts (A), 60 to 1 weight parts (condition is 100 weight parts for (A) and summation (B)), as modified polyolefin resin (C) based on (A) and summation (B) be being selected from of 0.1 to 50 weight part (C-1), (C-2) of 100 weight parts and (C-3) at least a, and its Izod shock strength is 100J/m or higher.

(11) a kind of automotive material parts that comprise according to the resin combination (D) of above-mentioned (1).

(12) a kind of home electric appliance material parts that comprises according to the resin combination (D) of above-mentioned (1).

(13) a kind of electrical/electronic material components that comprises according to the resin combination (D) of above-mentioned (1).

Effect of the present invention

The invention provides a kind of resin combination (D), it is characterized in that containing the aliphatic polyester resin (A) of 1 to 99 weight part, the polyolefin resin (B) of 99 to 1 weight parts (condition is 100 weight parts for (A) and summation (B)) and be the modified polyolefin resin (C) of 0.1 to 100 weight part of 100 weight parts based on (A) and summation (B), and from a kind of moulded product with excellent heat resistance and shock-resistance of resin combination (D) acquisition.

Embodiment

Hereinafter the present invention is described in detail.

[aliphatic polyester resin (A)]

The aliphatic polyester resin of Shi Yonging (A) is to contain the polyvalent carboxylic acid of diprotic acid and contain the polycondensate of the polyvalent alcohol of glycol, the polycondensate of alcohol acid, the ring-opening polymerization product and the analogue of lactone in the present invention.Particularly, for example, poly(lactic acid), polyglycolic acid, lactic acid-ethanol copolymer, poly butyric ester, poly-succsinic acid fourth diester, polyvinyl alcohol, cellulose acetate, poly-succsinic acid second diester, polycaprolactone, the sex change of polybutylene succinate adipate, the sex change of polybutylene succinate carbonate, poly-hexanodioic acid fourth diester-terephthalate, starch and analogue.As the aliphatic polyester resin among the present invention, the preferred use contained 50mol% or the more lactic acid units lactyl resin as polymeric constituent.

Term used herein " lactyl resin " is meant and comprises the polymer composition of polymkeric substance as main ingredient, its amount be at least 50mol% or more, be preferably 75mol% or more L-lactic acid units and/or D-lactic acid units, and it synthesizes by the polycondensation of lactic acid or the open loop polycondensation of rac-Lactide (it is the cyclic dimer of lactic acid).Wherein also can have other can with the monomer of lactic acid copolymerization by copolymerization.

More preferably wherein lactic acid units is the poly(lactic acid) of 100mol%.In addition, can be a kind of wherein outside the polymkeric substance that contains 50mol% or more lactic acid units, other resin, additive or analogue and polylactic acid based resin be the blended composition in can not the scope of the described polymer property of obvious damage.

As can with the monomer of lactic acid copolymerization, example has hydroxycarboxylic acid (for example oxyacetic acid, caproic acid and analogue), aliphatic polyol (for example butyleneglycol, ethylene glycol and analogue) and aliphatics polyvalent carboxylic acid (for example succsinic acid, hexanodioic acid and analogue).At the lactyl resin is under the situation of multipolymer, and the spread pattern of multipolymer can be random copolymers, alternating copolymer, segmented copolymer, graft copolymer and the analogue of arbitrary form.In addition, at least its part can with following material copolymerization: difunctionality or multi-functional polyol, for example ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol/propylene glycol copolymers, 1,3-butyleneglycol, 1,4-butyleneglycol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol, glycerine and TriMethylolPropane(TMP); Polyvalent isocyanate, xylilene vulcabond and 2 for example, 4-toluene di isocyanate; And polysaccharide, for example Mierocrystalline cellulose, cellulose acetate and ethyl cellulose, its at least a portion can be any form, for example linearity, ring-type, branch, starlike and three-dimensional netted structure.Therefore, without any restriction.

Further, the weight-average molecular weight of aliphatic polyester resin (A) is preferably 50,000 to 1,000,000, and preferred weight average molecular weight range is 100,000 to 500,000.

[polyolefin resin (B)]

The term that uses among the present invention " polyolefin resin (B) " is meant the polymkeric substance that comprises from the repeating unit of the alkene with 2 to 20 carbon atoms, comprises the homopolymer or the multipolymer of the alkene that is selected from the alkene with 2 to 20 carbon atoms particularly.In addition, the mixture that comprises these olefin polymers.When this polyolefinic segment had solid-tacticity, it can be isotactic polyolefin or syndiotaxy polyolefine.

As the alkene with 2 to 20 carbon atoms, example has alpha-olefin, cycloolefin, aromatic ethenyl compound, conjugated diene compound, non-conjugated diene compound and the analogue of linearity or side chain.Alpha-olefin as linearity or side chain, concrete, example has the alkene that has 2 to 20 carbon atoms, is preferably 2 to 10 carbon atoms, for example ethene, propylene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4,4-dimethyl-1-amylene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and 1-eicosylene.

As cycloolefin, example has the cycloolefin that has 3 to 20 carbon atoms, is preferably 5 to 15 carbon atoms, for example cyclopentenes, suberene, norbornylene, 5-methyl-2-norbornylene, tetracyclododecen and vinyl cyclohexane.As aromatic ethenyl compound, example has vinylbenzene, monoalkylated benzenes ethene or polyalkylbenzene ethene, for example alpha-methyl styrene, o-methyl styrene, a vinyl toluene, p-methylstyrene, adjacency pair position dimethyl styrene, adjacent ethyl styrene, an ethyl styrene and to ethyl styrene.

As conjugated diene compound, example has the conjugated diene compound that has 4 to 20 carbon atoms, is preferably 4 to 10 carbon atoms, for example 1,3-divinyl, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl isophthalic acid, 3-pentadiene, 1,3-pentadiene, 1,3-hexadiene and 1,3-octadiene.As the non-conjugated diene compound, example has and has 5 to 20 carbon atoms, be preferably the non-conjugated diene compound of 5 to 10 carbon atoms, for example 1, the 4-pentadiene, 1, the 4-hexadiene, 1, the 5-hexadiene, 1, the 4-octadiene, 1, the 5-octadiene, 1, the 6-octadiene, 1, the 7-octadiene, the 2-methyl isophthalic acid, the 5-hexadiene, the 6-methyl isophthalic acid, the 5-heptadiene, the 7-methyl isophthalic acid, the 6-octadiene, 4-ethylidene-8-methyl isophthalic acid, the 7-nonadiene, 4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems (DMDT), Dicyclopentadiene (DCPD), cyclohexadiene, two cyclooctadiene, methene norbornene, the 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornylene, 6-chloromethyl-5-isopropylidene-2-norbornylene, 2,3-diisopropylidene-5-norbornylene, 2-ethylidene-3-isopropylidene-5-norbornylene, with 2-propenyl-2, the 2-norbornadiene.

Further, can be by suitably selecting add-on and the kind to be added to the polyolefin resin (B) in the resin combination (D) that contains aliphatic polyester resin (A) and modified polyolefin resin (C), the balance of realization and shock-resistance, rigidity, thermotolerance and other character.In order to obtain the improved especially resin combination of thermotolerance and shock-resistance, preferably use the lactyl resin as aliphatic polyester resin, more preferably using weight-average molecular weight (Mw) is 2,000 to 1,000,000 poly(lactic acid).On the other hand, by selecting the low resin of second-order transition temperature (Tg), can obtain to have the resin combination of thermotolerance and shock-resistance combination as polyolefin resin.As used polyolefin resin, preferably using weight-average molecular weight (Mw) is 5,000 to 1,000,000, the fast at least a polyolefine of crystallization rate, it is selected from polyethylene, isotactic polyprophlene, atactic block polypropylene and analogue, more preferably isotactic polyprophlene.In addition, as the polyolefin resin that improves shock-resistance, the preferred multipolymer that is selected from alkene that uses with 2 to 20 carbon atoms.

[modified polyolefin resin (C)]

According to modified polyolefin resin of the present invention (C) is the multipolymer with following array structure: the polarity segment beyond polyolefine segment and the alkene is with block state and/or grafting state and/or disorganized form combination.Can change polarity segmental molecular chain length according to purpose, can be monomer or polymkeric substance.They can use separately or use as mixture.Modified polyolefin resin (C) is preferably the multipolymer with following array structure: the polyolefine segment, contain lactic acid as the segment of integral part and/or contain the acrylic acid series unit as the segment of integral part by covalent linkage with block state and/or grafting state and/or disorganized form combination, more preferably (C-1) hereinafter described, (C-2) and/or (C-3).In addition, they can use separately or use as mixture.(C-1)

(C-1) be multipolymer with following array structure: propenyl polyolefine segment (a) and contain lactic acid as the segment (b) of integral part by covalent linkage with block state and/or grafting combinations of states, the number-average molecular weight of wherein said propenyl polyolefine segment (b) is 1,000 to 100,000, the described lactic acid that contains is 1 as the number-average molecular weight of the segment (a) of integral part, 000 to 200,000, and described propenyl polyolefine segment (a) and the described lactic acid that contains consist of 10/90 to 90/10 as the weight of the segment (b) of integral part.

(C-2)

(C-2) be multipolymer with following array structure: contain the acrylic acid series unit as the segment of integral part and vinyl polyolefine segment by covalent linkage with block state and/or grafting state and/or disorganized form combination.

(C-3)

(C-3) be multipolymer with following array structure: contain the acrylic acid series unit as the segment of integral part and propenyl polyolefine segment by covalent linkage with block state and/or grafting state and/or disorganized form combination.

[modified polyolefin resin (C-1)]

Hereinafter the modified polyolefin resin (C-1) with following array structure according to the present invention is described: propenyl polyolefine segment (a) (hereinafter being called segment (a)) and contain lactic acid as the segment (b) (hereinafter being called segment (b)) of integral part by covalent linkage with block state and/or grafting combinations of states.

Segment (a) amount for 1mol% at least or more, be preferably 10mol% or more, more preferably 50mol% or more propylene be as component units.As other component, example has alpha-olefin, ethene and have the alpha-olefin of 4 to 20 carbon atoms for example, concrete example has 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene, 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and analogue.Can use it a kind of separately, perhaps be used in combination its two or more.As the segment of the modified polyolefin resin (C-1) that can be used for the improved resin combination of thermotolerance (D), particularly preferably, polyolefine segment (a) is the propenyl polyolefine.

The number-average molecular weight of segment (a) is 1,000 to 100,000, is preferably 2,000 to 80,000, more preferably 3,000 to 50,000.

Segment (b) amount for 1mol% at least or more, be preferably 10mol% or more, more preferably 50mol% or more lactic acid is as integral part, as other component, example has hydroxycarboxylic acid (for example oxyacetic acid and caproic acid), aliphatic polyol (for example butyleneglycol and ethylene glycol) and aliphatics polyvalent carboxylic acid (for example succsinic acid and hexanodioic acid).Can use it a kind of separately, perhaps be used in combination its two or more.As the segment of the modified polyolefin resin (C-1) that can be used for the improved resin combination of thermotolerance and shock-resistance (D), particularly preferably, containing lactic acid is the lactyl resin as the segment (b) of integral part.

The number-average molecular weight of segment (b) is 1,000 to 200,000, is preferably 2,000 to 100,000, more preferably 3,000 to 80,000.The molecular weight of segment (b) was greater than 200,000 o'clock, and the viscosity of modified polyolefin resin (C-1) increases, and is difficult to be dispersed in the resin combination (D).The molecular weight of segment (b) was less than 1,000 o'clock, and it is as the degradation of expanding material, and it is big that the fineness of dispersion of island phase becomes.

The weight of segment (a) and segment (b) consists of 1/99 to 90/10, is preferably 5/95 to 20/80, and more preferably 10/90 to 70/30.

Modified polyolefin resin (C-1) is meant the multipolymer with following array structure: segment (a) and segment (b) by covalent linkage, be preferably ester bond with block state and/or grafting combinations of states.

Following state represented in term " grafting " used among the present invention: in polymer chain, the position of covalent linkage can be main polymer chain, side chain and terminal optional position in the polymer chain, can be a plurality of positions by covalent bonds for monomer and/or polymkeric substance.

Manufacture method to modified polyolefin resin (C-1) does not specifically limit.Can use the conventional method of using.For example, by disclosed method among the JP-A-2001-270924 for example, can make propenyl series polyolefine segment wherein and contain lactic acid as the segment of integral part with block state bonded multipolymer.Promptly, in the method, make wherein at least one end and have the end that is combined with 13 family's elements on it or the polyolefine of unsaturated link(age) end, described end is changed into hydroxyl, aluminum oxide or analogue, rac-Lactide or lactic acid are carried out polymerization described in the presence of polyolefinic.

According to one of preferable production process of modified polyolefin resin of the present invention (C-1) is that the monomer that will contain rac-Lactide or lactic acid carries out polymerization in the presence of modified polyolefin resin, is grafted with the vinyl monomer (vinylmonomer) with hydroxyl in the described modified polyolefin resin on the polyolefin resin.

The modified polyolefin resin that is used as segment (a) among the present invention is a kind of grafted polyolefinic resin, and wherein polyolefin resin (a1) is grafted with the vinyl monomer (a2) with hydroxyl.Grafting amount with vinyl monomer (a2) of hydroxyl be polyolefin resin (a1) and vinyl monomer (a2) summation 0.1 to 10wt.%, be preferably 0.5 to 10wt.%, more preferably 1 to 10wt.%.

Polyolefin resin (a1) is preferably the propenyl polyolefine, and it can use the random or segmented copolymer of alfon or propylene and other alpha-olefin.The alpha-olefin of other and copolymerization of propylene is ethene or other alpha-olefin with 4 to 20 carbon atoms, its concrete example has 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene, 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and analogue.They can use it a kind of separately, perhaps are used in combination its two or more.

The fusing point (Tm) of the polyolefin resin (a1) by dsc measurement is 70 to 180 ℃, is preferably 90 to 170 ℃.

Go up the vinyl monomer (a2) that grafted has hydroxyl as polyolefin resin (a1), its example has, for example 2-hydroxyethyl methylacrylate (HEMA), 2-Hydroxyethyl acrylate, 2-Rocryl 410,2-Propylene glycol monoacrylate and analogue.In the middle of these, 2-hydroxyethyl methylacrylate (HEMA) most preferably.Vinyl monomer with hydroxyl can use it a kind of separately, perhaps is used in combination its two or more.

In order to make the segment (a) that uses among the present invention, can adopt ordinary method.After polyolefin resin (a1), vinyl monomer (a2) and radical polymerization initiator (c) mixing, for example, can carry out melt kneading with extrusion machine with hydroxyl.

Polyolefin resin (a1) and the blending ratio with vinyl monomer (a2) of hydroxyl are not done concrete qualification, as long as can obtain to have the polypropylene-based polyolefins segment (a) of above-mentioned grafting amount.But the ratio that usually requires to have the vinyl monomer (a2) of hydroxyl is per 100 weight part polyolefin resines (a1), 0.1 to 20 weight part, be preferably 0.5 to 15 weight part, 1 to 10 weight part more preferably.

As going up the used radical polymerization initiator (c) of vinyl monomer (a2) that graft polymerization has hydroxyl at polyolefin resin (a1); concrete example has 3; 5; 5-trimethyl acetyl superoxide (1); decoyl superoxide (2); caprinoyl superoxide (3); lauroyl peroxide (4); succinyl-superoxide (5); acetyl pexoxide (6); peroxide (2 ethyl hexanoic acid) tert-butyl ester (7); toluoyl superoxide (8); benzoyl peroxide (9); tert-butyl per(oxy)isobutyrate (10); 1; 1-two (t-butylperoxy)-3; 5; 5-trimethyl-cyclohexane (11); 1; 1-two (t-butylperoxy) hexanaphthene (12); the peroxy maleic acid tert-butyl ester (13); the peroxide lauric acid tert-butyl ester (14); peroxide-3; 5; 5-3-methyl cyclohexanol tert-butyl acrylate (15); pimelinketone superoxide (16); the peroxy isopropyl base carbonic acid tert-butyl ester (17); 2; 5-dimethyl-2; 5-two (benzoyl peroxy) hexane (18); tert-butyl peroxy acetate (19); 2; 2-two (t-butylperoxy) butane (20); t-butyl per(oxy)benzoate (21); 4; 4-two (t-butylperoxy) n-butyl pentanoate (22); peroxide m-phthalic acid di tert butyl carbonate (23); methyl-ethyl-ketone peroxide (24); α; α '-two (t-butyl peroxy sec.-propyl) benzene (25); dicumyl peroxide (26); 2; 5-dimethyl-2; 5-two (t-butylperoxy) hexane (27); tertiary butyl cumyl peroxide (28); di-isopropylbenzene hydroperoxide (29); ditertiary butyl peroxide (30); p-methane hydroperoxide (31); 2; 5-dimethyl-2; 5-two (t-butylperoxy) hexin-3 (32); 1; 1; 3; 3-tetramethyl butyl-hydrogen peroxide (33); 2; 5-dimethylhexane-2,5-dihydro-peroxidase (34); cumene hydroperoxide (35); tert-butyl hydroperoxide (36); and analogue.In the middle of these, particularly preferably be compound (12) to (36).

The combined amount of radical polymerization initiator (c) is per 100 weight part polyolefin resines (a1), 0.01 to 10 weight part, be preferably 1 to 10 weight part, 1 to 5 weight part more preferably.The combined amount of radical polymerization initiator (c) is during less than 0.01wt.%, have the graft polymerization of vinyl monomer (a2) of hydroxyl and polyolefin resin (a1) go up free radical cause the formation of point then can be not enough.As a result, be difficult to obtain on processing characteristics, to show the polypropylene-based polyolefins segment (a) of enough improved effects.In addition, when surpassing 10 weight parts, (c) is excessive for radical polymerization initiator, and therefore, the molecular weight of polypropylene-based polyolefins segment (a) reduces, so it is difficult to be committed to practical application.

The existence that is included in polypropylene-base series polyolefine segment (a) according to the manufacture method of modified polyolefin resin of the present invention (C-1) will contain rac-Lactide or the lactic acid method as the monomer polymerization of main ingredient down.Because the polymerization of rac-Lactide, lactic acid or other monomer, form modified polyolefin resin (C-1) with following array structure by contained hydroxyl in the polypropylene-based polyolefins segment (a): contain lactic acid as the segment (b) of integral part and propenyl polyolefine segment (a) by covalent linkage with block state and/or grafting combinations of states.

As other monomer outside rac-Lactide and the lactic acid, can use cyclic cyclic ester (lactone) for example caprolactone, propiolactone, butyrolactone and hydroxyl alkane such as hydroxyl butane and hydroxy propane.

The monomeric combined amount of outside rac-Lactide, lactic acid and rac-Lactide and the lactic acid other is per 100 weight part propenyl polyolefine segments (a), 1 to 10,000 weight part, be preferably 5 to 5,000 weight parts, 10 to 1,000 weight parts more preferably.

When carrying out the monomeric polymerization of rac-Lactide, lactic acid or other, preferably use solvent.For example, use aliphatic hydrocarbon, as hexane, heptane and decane; Alicyclic hydrocarbon is as pentamethylene and hexanaphthene; Aromatic hydrocarbon is as benzene, toluene and dimethylbenzene; The ether series solvent is as diethyl ether, dioxane, tetrahydrofuran (THF) (THF) and diglyme; And analogue.These solvents can be used alone, and perhaps are used in combination two or more.Remove easily after finishing from solubleness, temperature of reaction, speed of reaction, the reaction of rac-Lactide or lactic acid and desolvate and similar aspect is considered, preferably use aromatic hydrocarbon and ether series solvent.Preferred especially dimethylbenzene and toluene.The consumption of solvent is selected from propenyl polyolefine segment (a) and rac-Lactide or lactic acid gross weight 0.1 to 20 times.Preferred especially 0.5 to 3 times.

In the manufacture method of modified polyolefin resin according to the present invention (C-1), when in the presence of propenyl series polyolefine segment (a), making rac-Lactide or lactic acid polymerizes, can use conventional catalyst as catalyzer.Preferred tin series catalysts or aluminum-based catalyst.During the rac-Lactide polymerization, preferably use stannous octoate, its consumption be rac-Lactide 0.01 to 5wt.%.

Polymerization temperature suitably is selected from 60 to 230 ℃.Preferably, temperature is 100 to 200 ℃.For example, when using dimethylbenzene to make rac-Lactide and modified polyolefin resin reaction as solvent, stannous octoate as catalyzer, temperature of reaction is preferably about 110 to 150 ℃.

On the other hand, modified polyolefin resin (C-1) can also obtain by following method: will have the vinyl monomer of hydroxyl and contain rac-Lactide or lactic acid carries out polymerization as the monomer of main ingredient, obtain having vinyl group and contain the segment (b2) of lactic acid as integral part, it is mixed with polyolefin resin (a1) and radical polymerization initiator (c), and use for example extrusion machine melt kneading.

For example, can pass through vinyl monomer (a2) polymerization, obtain having vinyl group and contain the segment (b2) of lactic acid as integral part with rac-Lactide, lactic acid or other monomer and 0.001 to 20 weight part of 100 weight parts.

As other monomer outside rac-Lactide and the lactic acid, can use cyclic cyclic ester (lactone) for example caprolactone, propiolactone, butyrolactone and hydroxyl alkane acid such as hydroxybutyric acid and hydroxy-propionic acid.

When carrying out the monomeric polymerization of rac-Lactide, lactic acid or other, can use solvent.For example, use aliphatic hydrocarbon, as hexane, heptane and decane; Alicyclic hydrocarbon is as pentamethylene and hexanaphthene; Aromatic hydrocarbon is as benzene, toluene and dimethylbenzene; The ether series solvent is as diethyl ether, dioxane, tetrahydrofuran (THF) (THF) and diglyme; And analogue.These solvents can be used alone, and perhaps are used in combination two or more.Remove easily after finishing from solubleness, temperature of reaction, speed of reaction, the reaction of rac-Lactide or lactic acid and desolvate and similar aspect is considered, preferably use aromatic hydrocarbon and ether series solvent.Preferred especially dimethylbenzene and toluene.The consumption of solvent is selected from vinyl monomer (a2) and rac-Lactide or lactic acid gross weight 0.1 to 20 times.Particularly preferably, consumption is 0.5 to 3 times.

Having vinyl group and contain in the manufacture method of lactic acid as the segment (b2) of integral part, when in the presence of vinyl monomer (a2), making rac-Lactide or lactic acid polymerizes, can use conventional catalyst as catalyzer according to of the present invention.Preferred tin series catalysts or aluminum-based catalyst.During the rac-Lactide polymerization, preferably use stannous octoate, its consumption be rac-Lactide 0.01 to 5wt.%.

Polymerization temperature suitably is selected from 60 to 230 ℃.Preferably, temperature is 100 to 200 ℃.For example, when using dimethylbenzene to make rac-Lactide and vinyl monomer (a2) reaction as solvent, stannous octoate as catalyzer, temperature of reaction is preferably about 120 to 180 ℃.

Next, mix by the same way as that obtains polypropylene-base alkene segment (a) with polyolefin resin (a1) as the segment (b2) of integral part, can obtain modified polyolefin resin (C-1) by having vinyl group and containing lactic acid.

Polyolefin resin (a1) is preferably the propenyl polyolefine, can use the random or segmented copolymer of alfon or propylene and other alpha-olefin.The alpha-olefin of other and copolymerization of propylene is ethene or other alpha-olefin with 4 to 20 carbon atoms, its concrete example has 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene, 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and analogue.They can use it a kind of separately, perhaps are used in combination its two or more.

Polyolefine (a1) and have vinyl group and contain lactic acid and do not do concrete qualification as the blending ratio of the segment (b2) of integral part.But, usually requiring to have hydroxyl groups and containing lactic acid is per 100 weight part polyolefin resines (a1) 1 to 10 as the ratio of the segment (b2) of integral part, 000 weight part, be preferably 5 to 5,000 weight part, 10 to 1,000 weight parts more preferably.

As having vinyl group; and contain the radical polymerization initiator (c) that uses in the melt kneading of lactic acid as the segment (b2) of integral part and polyolefin resin (a1); concrete example has 3; 5; 5-trimethyl acetyl superoxide (1); decoyl superoxide (2); caprinoyl superoxide (3); lauroyl peroxide (4); succinyl-superoxide (5); acetyl pexoxide (6); peroxide (2 ethyl hexanoic acid) tert-butyl ester (7); toluoyl superoxide (8); benzoyl peroxide (9); tert-butyl per(oxy)isobutyrate (10); 1; 1-two (t-butylperoxy)-3; 5; 5-trimethyl-cyclohexane (11); 1; 1-two (t-butylperoxy) hexanaphthene (12); the peroxy maleic acid tert-butyl ester (13); the peroxide lauric acid tert-butyl ester (14); peroxide-3; 5; 5-3-methyl cyclohexanol tert-butyl acrylate (15); pimelinketone superoxide (16); the peroxy isopropyl base carbonic acid tert-butyl ester (17); 2; 5-dimethyl-2; 5-two (benzoyl peroxy) hexane (18); tert-butyl peroxy acetate (19); 2; 2-two (t-butylperoxy) butane (20); t-butyl per(oxy)benzoate (21); 4; 4-two (t-butylperoxy) n-butyl pentanoate (22); peroxide m-phthalic acid di tert butyl carbonate (23); methyl-ethyl-ketone peroxide (24); α; α '-two (t-butyl peroxy sec.-propyl) benzene (25); dicumyl peroxide (26); 2; 5-dimethyl-2; 5-two (t-butylperoxy) hexane (27); tertiary butyl cumyl peroxide (28); di-isopropylbenzene hydroperoxide (29); ditertiary butyl peroxide (30); p-methane hydroperoxide (31); 2; 5-dimethyl-2; 5-two (t-butylperoxy) hexin-3 (32); 1; 1; 3; 3-tetramethyl butyl-hydrogen peroxide (33); 2; 5-dimethylhexane-2,5-dihydro-peroxidase (34); cumene hydroperoxide (35); tert-butyl hydroperoxide (36); and analogue.In the middle of these, particularly preferably be compound (12) to (36).

The combined amount that requires radical polymerization initiator (c) for based on polyolefin resin (a1) and contain lactic acid as 0.01 to 10 weight part of the summation of the segment (b2) of integral part, be preferably 0.1 to 10 weight part, 0.2 to 5 weight part more preferably.

As above, can make modified polyolefin resin (C-1) with following array structure: polypropylene-based polyolefins segment (a) and contain lactic acid as the segment (b) of integral part by covalent linkage with block state and/or grafting combinations of states, this (C-1) is suitable for use as the expanding material of the resin combination (D) that comprises aliphatic polyester resin (A) and polyolefin resin (B).

For example, by the molecular weight of resulting polymers, solubleness or spectroscopy analysis in organic solvent, can judge according to modified polyolefin resin of the present invention (C-1) whether contain multipolymer with following array structure: polypropylene-based polyolefins segment (a) and contain lactic acid as the segment (b) of integral part by covalent linkage with block state and/or grafting combinations of states.That is, can think by the following fact and make required segmented copolymer: the value that the molecular weight of the multipolymer that obtains by method of the present invention demonstrates is higher than the molecular weight of polypropylene-based polyolefins segment (a) used when making rac-Lactide or lactic acid polymerizes; The solubility behavior to organic solvent that the copolymer sheet that obtains by method of the present invention reveals is different from polylactic acid based resin or the used polyolefine solubility behavior to organic solvent; Perhaps the end structure of the multipolymer that obtains by method of the present invention with NMR (Nuclear Magnetic Resonance) spectrum (NMR) analyzing and testing to from propenyl polyolefine segment (a) with contain the peak of the chemical bond between the segment (b) of lactic acid.

In addition, can measure by ordinary method according to the molecular weight of modified polyolefin resin of the present invention (C-1).For example, can measure as the gel permeation chromatography (GPC) of solvent by using dichlorobenzene.In addition, propenyl polyolefine segment (a) and contain lactic acid and can learn by ordinary method in the modified polyolefin resin (C-1) as the multipolymer proportion of composing between the segment (b) of integral part.For example,, in the 2-dichlorobenzene, measure proton N MR spectrum down, can learn at 120 ℃ by multipolymer being dissolved in deuterium for 1.Each segmental molecular weight can be learnt with each segmental proportion of composing by the molecular weight of modified polyolefin resin (C-1).For example, in the multipolymer number-average molecular weight is 40,000 and propenyl polyolefine segment (a) and to contain lactic acid be under 1: 1 the situation as the proportion of composing of the segment (b) of integral part, the molecular weight of propenyl polyolefine segment (a) is 20,000, containing lactic acid is 20,000 as the molecular weight of the segment (b) of integral part.

[modified polyolefin resin (C-2)]

Modified polyolefin resin among the present invention (C-2) is the multipolymer with following array structure: contain the acrylic acid series unit as the segment of integral part and vinyl polyolefine segment by covalent linkage with block state and/or grafting state and/or disorganized form combination.In containing the segment of acrylic acid series unit as integral part, must contain 50mol% or more acrylic acid series unit at least, preferably contain 75mol% or more.As the acrylic acid series unit, preferred acrylic acid units, as preferred embodiment, example has methyl methacrylate units, methyl acrylate unit, ethyl propenoate unit and butyl acrylate units.Can comprise multiple in these components.

In addition, used term " vinyl polyolefine " is meant and contains 1mol% at least or more ethylene unit are formed unit as polymkeric substance polyolefine among the present invention.When 1mol% or more ethene generation copolymerization, can select middle 2 kinds of describing of polyolefin resin (B) or multiple monomer to carry out copolymerization, under the situation of multipolymer, its structure can be any in random copolymers, segmented copolymer, graft copolymer and the analogue.

In addition, the structure of modified polyolefin resin (C-2) can be: contain the acrylic acid series unit and take in statistic copolymer, segmented copolymer, graft copolymer and the similar type any as the segment of integral part and vinyl polyolefine segment, do not impose any restrictions.

In addition, containing the acrylic acid series unit in the modified polyolefin resin (C-2) can learn by ordinary method as the segment of integral part and the multipolymer proportion of composing of vinyl polyolefine segment.For example,, in the 2-dichlorobenzene, measure proton N MR spectrum down, can learn at 120 ℃ by multipolymer being dissolved in deuterium for 1.The composition of modified polyolefin resin (C-2) can be according to purpose and appropriate change.Consist of: contain the acrylic acid series unit and be preferably 10/90 to 90/10, more preferably 20/80 to 80/20 as the segment of integral part and the part by weight of vinyl polyolefine segment.

[modified polyolefin (C-3)]

In the present invention, modified polyolefin resin (C-3) is the multipolymer with following array structure: contain the acrylic acid series unit as the segment of integral part and propenyl polyolefine segment by covalent linkage with block state and/or grafting state and/or disorganized form combination.In containing the segment of acrylic acid series unit as integral part, must contain 50mol% or more acrylic acid series unit at least, preferably contain 70mol% or more.As the acrylic acid series unit, preferred acrylic acid units, as preferred embodiment, example has methyl methacrylate units, methyl acrylate unit, ethyl propenoate unit and butyl acrylate units.Can comprise multiple in these components.

In addition, used term " propenyl polyolefine " is meant and contains 1mol% at least or more propylene units are formed unit as polymkeric substance polyolefine among the present invention.

The structure of propenyl polyolefine segment is meant the polymkeric substance that comprises from the repeating unit of the alkene with 2 to 20 carbon atoms, identical with the situation of polyolefin resin (B), it is in particular the homopolymer or the multipolymer of the alkene that is selected from the alkene with 2 to 20 carbon atoms.Have under the situation of three-dimensional regularity at this polyolefine segment, it can be in isotactic polyolefin, the syndiotaxy polyolefine any, under the situation of multipolymer, its structure can be taked any in random copolymers, segmented copolymer, graft copolymer and the analogue.

In addition, containing the acrylic acid series unit in the modified polyolefin resin (C-3) can learn by ordinary method as the segment of integral part and the multipolymer proportion of composing of propenyl polyolefine segment.For example,, in the 2-dichlorobenzene, measure proton N MR spectrum down, can learn at 120 ℃ by multipolymer being dissolved in deuterium for 1.The composition of modified polyolefin resin (C-3) can be according to purpose and appropriate change.Consist of: contain the acrylic acid series unit and be preferably 10/90 to 90/10, more preferably 20/80 to 80/20 as the segment of integral part and the part by weight of propenyl polyolefine segment

[resin combination (D)]

According to resin combination of the present invention (D) is to contain aliphatic polyester resin (A), polyolefin resin (B), and the resin combination of modified polyolefin resin (C), proportion of composing as resin combination shown in the present (D) is: the polyolefin resin (B) of aliphatic polyester resin of 1 to 99 weight part (A) and 99 to 1 weight parts (condition is that (A) and summation (B) are 100 weight parts), modified polyolefin resin (C) is 0.1 to 100 weight part, be preferably the aliphatic polyester resin (A) of 10 to 90 weight parts and the polyolefin resin (B) of 90 to 10 weight parts (condition is that (A) and summation (B) are 100 weight parts), modified polyolefin resin (C) is 0.5 to 50 weight part, the polyolefin resin (B) of aliphatic polyester resin of 20 to 80 weight parts (A) and 80 to 20 weight parts (condition is 100 weight parts for (A) and summation (B)) more preferably, modified polyolefin resin (C) is 1 to 20 weight part.

By comprising modified polyolefin resin (C), the consistency between aliphatic polyester resin (A) and the polyolefin resin (B) is improved, and forms the resin combination (D) of the two good distribution.Consistency and dispersed improvement can confirm by following method, for example, observe the cross section of resin combination with electron microscope or analogue.By adding modified polyolefin resin (C), can confirm that arbitrary size (diameter, thickness and analogue) that all becomes mutually of polyolefin resin (B) or aliphatic polyester resin (A) is 100 μ m or littler.In the preferred case, it is 20 μ m or littler, and under preferred situation, it is 5 μ m or littler.By adding modified polyolefin resin (C), consistency between aliphatic polyester resin (A) and the polyolefin resin (B) increases, the dispersiveness of island in resin combination (D) improved, thereby not only the thermotolerance of aliphatic polyester resin (A) is improved, and shock-resistance, tensile elongation, tensile strength, flexural strength, low temperature durability energy, tear strength and similarity are also improved.

Particularly, in order to obtain the improved resin combination of thermotolerance (D), preferred polyolefine (the Mw:5 that uses at least a crystallization rate height, is selected from polyethylene, isotactic polyprophlene, isotactic block polypropylene and analogue, 000 to 1,000,000) as polyolefin resin (B), and use poly(lactic acid) (Mw:2,000 to 1,000,000) as aliphatic polyester resin (A).

As polyolefin resin (B), the intrinsic viscosity [η] that records in perhydronaphthalene under 135 ℃ is 0.01 to 15dl/g, is preferably 0.1 to 10dl/g.Can change the kind of polyolefin resin (B) according to its purpose.Under the situation of improving the aliphatic polyester shock-resistance, the second-order transition temperature (Tg) that records by DSC is preferably 0 ℃ or lower, more preferably-30 ℃ or lower.In order to improve the thermotolerance of aliphatic polyester, under poly situation, the fusing point (Tm) that records by DSC is preferably 70 to 130 ℃, under polyacrylic situation, the fusing point (Tm) that records by DSC is preferably 70 to 180 ℃, more preferably 100 to 170 ℃, more preferably 120 to 160 ℃.

Particularly, use polypropylene as polyolefin resin (B) to improve under the stable on heating situation preferred three-dimensional regularity height and the wide polypropylene of molecular weight distribution.Particularly, preferably isotaxy five company headquarters's branches (isotactic pentad fraction) (mmmm part) of recording of the 13C-NMR spectrum of the component (X) by being insoluble to 23 ℃ p-Xylol are 97% or more and be 6 to 20 polypropylene by the molecular weight distribution that is expressed as Mw/Mn that gel permeation chromatography (GPC) records.

[additive]

According to purpose (for example, improve plasticity-, secondary workability, degraded character, tensile strength, thermotolerance, stability in storage, weathering resistance and flame retardant resistance), can in resin combination according to the present invention (D), add other resin or polymkeric substance or multiple additives.As other resin or the polymkeric substance that add, example has polyolefine, ethenoid resin, polystyrene, polymeric amide, acrylic resin, polyphenylene sulfide, polyether-ether-ketone resin, polyester, polysulfones, polyphenylene oxide, polyimide, polyetherimide, acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-, conjugated diene rubber, styrene resin, resol, melamine resin, vibrin, silicone resin, Resins, epoxy and the analogue of non-modified.Can add in these resins one or both or more kinds of.Preferably, be styrenerubber, particularly, it is styrene-butadiene-styrene SBS rubber, styrene butadiene-butylene-styrene SBBS rubber, styrene-ethylene-butylene-styrene SEBS rubber and with maleation modified SEBS, maleation modification SBBS, imino-modified SEBS and the imino-modification SBBS or the analogue of acid/base-modified acquisition.Further preferably, require styrene-ethylene-butylene-styrene SEBS rubber and styrene butadiene-butylene-styrene SBBS rubber into the imido grpup modification.Preferably, the addition of other resin or polymkeric substance is 0.1 to 30 weight part based on 1 to 99 weight part aliphatic polyester resin (A) and 99 to 1 weight part polyolefin resines (B) (condition is that (A) and summation (B) are 100 weight parts), and it is within the scope that can not damage the object of the invention according to the purposes purpose.

As various additives, example has softening agent, antioxidant, UV light absorber, thermo-stabilizer, fire retardant, internal mold release, inorganic additives, static inhibitor, moistened surface modifying agent, burns auxiliary agent, pigment, dyestuff, nucleator, lubricant, crude substance and analogue.Preferred example is a softening agent.As concrete softening agent, example has glycerol acetate, triethylene-glycol diacetate, acetyl triethyl citrate, tributyl acetylcitrate, Uniflex DBS and analogue.

In addition, in T pattern tool extrusion molding,, can also add inorganic additives or lubricant (aliphatic carboxylic acid amide) for the anti-blocking effect that improves film or sheet material or smooth.As inorganic additives, example has silicon-dioxide, mica, talcum, glass fibre, granulated glass sphere, kaolin, kaolinite, barium sulfate, calcium sulfate, magnesium hydroxide, wollastonite, carbon fiber, ca silicate fibre, contains oxygen sal epsom fiber, potassium titanate fiber, calcium sulfite, white carbon black, clay, montmorillonite, titanium oxide, zinc oxide and analogue.Particularly, preferred mica, talcum, glass fibre, carbon fiber and lime carbonate.Can use a kind of in them, perhaps two or more mixture.Particularly, by using glass fibre as inorganic additives, expectation can improve the thermotolerance of resin combination.In addition, as organic additive, example has starch and derivative thereof, Mierocrystalline cellulose and derivative thereof, paper pulp and derivative thereof, paper and derivative thereof, whole meal flour, beans processing of waste (bean cured refuse), chaff, coconut husk, coffee cake (coffee cake), protein, the O-phthalic acidic group, the polynary acidic group of aliphatics, glyceryl, citric acid-based, the low molecular weight substance of ethylene glycol and alkylene is as softening agent, pet fiber, PEN fiber and Kevlar fiber are as organic fibre, and analogue.Particularly, by using softening agent, the second-order transition temperature (Tg) of aliphatic polyester resin (A) reduces, thereby can estimate that thermotolerance, shock-resistance, ductility and similarity are improved.In addition, by using organic fibre, can estimate stable on heating improvement.Can use a kind of in them, perhaps two or more mixture.

Preferably, the addition of each in these various additives is 0.1 to 30 weight part based on 1 to 99 weight part aliphatic polyester resin (A) and 99 to 1 weight part polyolefin resines (B) (condition is that (A) and summation (B) are 100 weight parts), and it is within the scope that can not damage the object of the invention according to the purposes purpose.

[manufacture method of resin combination (D)]

Usually, as for the resin combination (D) of aliphatic polyester resin (A), polyolefin resin (B) and modified polyolefin resin (C) and the manufacture method that wherein is added with the composition of other properties-correcting agent as required of containing according to the present invention, can suitably adopt the ordinary method of making the resin combination that comprises thermoplastic resin.For example, can adopt following method: use homogenizer, low-speed mixer or similar machine to carry out uniform mixing in advance, under melting point resin or higher temperature, carry out melt kneading with having single screw rod of enough kneading abilities or multiple screw extruder then; The method of when fusion, mixing and mediating; In solution, mix, remove then the method for desolvating; Or similar approach.

The manufacturing of resin combination (D) can be carried out before the moulded product moulding, and perhaps manufacturing and moulding can be carried out simultaneously.Under the situation of making resin combination before the moulding, that the shape of resin combination is preferably usually is granular, bar-shaped, powder or analogous shape.

[moulded product of resin combination (D)]

The manufacture method that obtains moulded product (E) from the resin combination (D) that contains aliphatic polyester resin (A), polyolefin resin (B) and modified polyolefin resin (C) according to the present invention can adopt the conventional method of using.For example, can use following method manufacturing.

(1) in extrusion molding, resin combination according to the present invention is carried out molding with general T pattern tool single-lead-screw extruding briquetting machine, thereby form film or sheet material.

(2) in injection moulding, will be softening according to the particle fusion of resin combination of the present invention, the mould of packing into obtains moulded product in 20 to 90 seconds mold cycle.

(3) in blow moulding (injection blow molding, stretch-blow or direct blow moulding), for example, in the injection blow molding method, will be according to the particle fusion of resin combination of the present invention, the mould of packing into obtains pre-shaped articles with common injection blow molding machine.With the pre-shaped articles heating once more in baking oven (process furnace) that obtains, and place mould to remain under the specified temp, import pressurized air and carry out blowing, thereby can carry out molded blow molded bottle.

(4) in vacuum forming/vacuum pressure method of forming, use film by the method molding identical or sheet material as pre-shaped articles with above-mentioned (1) extrusion molding.The pre-shaped articles that obtains is heated to softening, uses in the common mould of vacuum forming machine under remaining on specified temp it is carried out vacuum forming or vacuum pressure moulding, thus can the molding moulded product.

(5) in laminate moulding, can obtain moulded laminated product by following method: film that will obtain by above-mentioned extrusion molding (1) or sheet material and other matrix are by the method for tackiness agent or heated lamination; The extruding layer platen press of on matrix such as paper, metal or plastics, the fused resin directly being extruded from T pattern tool by the method identical with above-mentioned extrusion molding (1); Forcing machine difference fusion every kind of resin combination of the present invention and analogue with independent compile the coetrusion that flow to die head and extrude simultaneously; Co-extrusion laminating method in conjunction with these methods; And similar approach.

(6) in flat filament (tape yam) moulding method, to be cut into specific width by the method identical molded film or sheet material with above-mentioned extrusion molding (1), single shaft is to adding hot stretched in 60 to 140 ℃ temperature range, can further fix in this case at 80 to 160 ℃ temperature temperature range internal heating, thus can the molding moulded product.

(7) in the yarn moulding method, yarn can be by using the forcing machine fusing and obtaining from the melt spinning method that spinning nozzle is emitted under 150 to 240 ℃ temperature.If necessary, yarn can come molding to adding hot stretched by single shaft in 60 to 100 ℃ temperature range, can further fix at 80 to 140 ℃ temperature range internal heating in this case.

(8) in non-woven moulding method, can come the molding moulded product by heat pressure adhesive (span bond) method or melt-blown method.In thermocompression bonded is legal, carry out melt-spinning by the mode identical by spinnert with above-mentioned yarn moulding method (7), the air intake duct tractive that use is positioned over the spinning nozzle bottom forms net, accumulate on the face of holding back (trapping face), by grain roller and straightening roller it is carried out engage pressure and heat bonding, thereby obtain supatex fabric.In the melt-blown method, can contact with the high speed hot gas that blows from the hot gas outlet by the molten resin that spinnert is emitted, form fine-fibered, accumulate on the mobile upholder, thereby obtain supatex fabric.

By the resin combination (D) that contains aliphatic polyester resin (A), polyolefin resin (B) and modified polyolefin resin (C) according to the present invention, provide a kind of with only be mixed with aliphatic polyester resin (A) and compare the more excellent moulded product of thermotolerance with the resin combination of polyolefin resin (B).The softening temperature of moulded product is 60 ℃ or higher, is preferably 65 ℃ or higher, and more preferably 70 ℃ or higher, it can be applied to the in fact inefficient field of aliphatic polyester resin (A), particularly conventional poly(lactic acid).

Further, by the resin combination (D) that contains aliphatic polyester resin (A), polyolefin resin (B) and modified polyolefin resin (C) according to the present invention, provide a kind of with only be mixed with aliphatic polyester resin (A) and compare the more excellent moulded product of shock-resistance with the resin combination of polyolefin resin (B).The Izod shock strength of moulded product is 100J/m or higher, is preferably 130J/m or higher, and it can be applied to the in fact inefficient field of aliphatic polyester resin (A), particularly conventional poly(lactic acid).

Further, the heat-drawn wire of moulded product (HDT) is 60 ℃ or higher, is preferably 65 ℃ or higher, and more preferably 70 ℃ or higher, it can be applied to the in fact inefficient field of aliphatic polyester resin (A), particularly conventional poly(lactic acid).

[measuring methods of various physical propertiess]

[intrinsic viscosity]

In the present invention, intrinsic viscosity [η] is a value of using the perhydronaphthalene solvent to record down at 135 ℃.That is, the granular bead of about 20mg is dissolved in the 15ml perhydronaphthalene, in 135 ℃ oil bath, measures specific viscosity η sp.5ml perhydronaphthalene solvent joined in the perhydronaphthalene solution dilute, measure specific viscosity η sp then in the same manner.This dilution operation further repeats twice, and the η sp/C pH-value determination pH that concentration (C) is extrapolated at 0 o'clock is an intrinsic viscosity.

[softening temperature]

In the present invention, the measuring method of softening temperature is meant and uses TMA5200 (SeikoInstruments Inc. product), uses the pressure head of diameter 1mm to impose 50g/cm ²Load, under the intensification condition of 2 ℃/min, under nitrogen gas stream, measure, read the infiltration temperature, this temperature is as texturing temperature (JIS K7196).

[Izod shock strength]

In the present invention, the Izod shock strength is meant the breach Izod shock strength that records according to ASTM D256 under 23 ℃.

[melt flow rate (MFR) (MFR)]

In the present invention, the following mensuration of melt flow rate (MFR) (MFR).That is, the hole of satisfying prescribed level among the JIS K7210 is installed on the automatic MFR determinator that Tester Sangyo Co. makes according to JIS K7210, the temperature of cylinder (sample places its part) is increased to 190 ℃ or 230 ℃ and keeps.Sample places cylinder, preheating 6 minutes.After the preheating, the load that imposes 2.16Kg is extruded sample, calculates per example weight that was squeezed out in 10 minutes, with it as MFR.

[weight-average molecular weight (Mw) and number-average molecular weight (Mn)]

Use the product G PC-150C of Waters Co. to carry out following measurement.Separator column is TSKgelGMH6-HT and TSKgel GMH6-HTL, and the size of every post is internal diameter 7.5mm, long 600mm, and column temperature is 140 ℃.As moving phase, use orthodichlorobenzene (Wako PureChemicals Industries, Ltd.) and the antioxidant BHT of 0.025wt.% (TakedaPharmaceutical Company Limited), flow velocity is 1.0ml/min, sample concentration is 0.1wt.%, sample size is 500 μ l, uses differential refractometer as detector.About polystyrene standards, use Tosoh Corporation product to be used for Mw＜1,000 and Mw＞4 * 10 ⁶Molecular weight, use the product of Pressure Chemical Co. to be used for 1,000＜Mw＜4 * 10 ⁶Molecular weight.Molecular weight is by unifying correction (universal correction) and being transformed into the value that polystyrene obtains.

[heat-drawn wire (HDT)]

In the present invention, heat-drawn wire (HDT) is to be that 2 ℃/min, test pressure are the deflection that records testing plate under the condition of the 0.451MPa temperature when reaching 0.254mm at temperature rise rate, used along limit test length of a film 128mm, wide 12.8mm, thick 3.2mm, the thermal distortion test machine HDA that uses YasudaSeiki Co. to make according to ASTM D647.

The resin dispersion of the moulded product that is obtained by the resin combination (D) that contains aliphatic polyester resin (A), polyolefin resin (B) and modified polyolefin resin (C) according to the present invention is good, compare with the moulded product of the conventional compositions of polyolefin resin (B) with comprising aliphatic polyester resin (A), its balance of properties of intensity, transparency and similarity and stable aspect very excellent.

[application of resin combination (D)]

Resin combination of the present invention (D) can carry out molding by above-mentioned various working methods, goes for multiple use, and is not subjected to concrete restriction.Further, these moulded products can be used for multiple use, for example trolley part, home electric appliance material parts, Electrical and Electronic parts, building slab, civil engineering work member, agricultural materials, daily necessities, various film, air-permeating film or sheet material, the foamed products that is suitable for general industry purposes and recreational use, yarn, textiles, medical or sanitary material and analogue.Preferably, it can be used for automotive material parts, home electric appliance material parts and the Electrical and Electronic parts of requirement thermotolerance and shock-resistance.Concrete example has the parts that are developed to conventional use resin component in the trolley part material is used, as Qianmen and wheel cover; In home electric appliance material parts is used, be developed to the package member of product such as Personal Computer, stereophone and mobile telephone; In using, the Electrical and Electronic parts are developed to reflecting material film and sheet material and polarization film and sheet material; And analogue.

Embodiment

Hereinafter the present invention further is specifically described, but the present invention is not limited to these embodiment based on embodiment.

[making embodiment 1]

[synthesizing the modified polypropylene resin (PP-HEMA) that 2-hydroxyethyl methylacrylate (HEMA) graft reaction takes place on it]

With (MFR:230 ℃ of 100 weight part melt flow rate (MFR), 2,160g) be 0.02g/10min, the intrinsic viscosity [η] that records in 135 ℃ of perhydronaphthalenes is 10.5dl/g, and the accumulation pore volume is that the alfon powder of 0.25cc/g and 3 weight part 2-hydroxy methyl methacrylate (HEMA) and 3 weight part t-butyl per(oxy)benzoates (PBZ:JOF Corporation product) carry out dry mixed with the Henschel mixing machine, use twin screw kneader (Technobell down at 210 ℃ then, ZSK-30) carry out fusion and modify, obtain modified polypropylene resin (hereinafter being called PP-HEMA) particle.The number-average molecular weight that this modified polypropylene resin records by GPC (Mn) is 31,000.MFR is 450g/10min, and [η] is 0.80dl/g, remove unreacted HEMA purifying after, recording HEMA grafting amount by NMR is 1.7wt.%.

[making embodiment 2]

[synthetic end has the polypropylene (PP-OH) of hydroxyl]

With Mitsui Chemicals, the polypropylene ([η]=7.6) that Inc. makes is carrying out thermal decomposition process with plastmill under 360 ℃ under nitrogen atmosphere.The number-average molecular weight (Mn) of the polymkeric substance that obtains by processing is 27,600.Analyze confirmation from IR, have 0.74 vinylidene on each polymer chain.

To the internal volume that agitator is housed is 1, adds the 800ml decane in the glass reactor of 000ml and the end that above obtains has the olefin polymer (25.0g) of unsaturated link(age), fully replaces with nitrogen, is increased to 140 ℃, the dissolved olefin polymkeric substance.After this, add diisobutyl aluminium hydride (9mmol), mixture was handled 6 hours in nitrogen atmosphere under 140 ℃.Solution is cooled to 100 ℃, adds Epicholorohydrin (4.5ml) in reactor, contacts 1 hour down at 100 ℃.Reaction soln is poured in methyl alcohol (1.5L)/acetone (1.5L) mixing solutions that contains 30ml1N hydrochloric acid.After at room temperature stirring 30 minutes, the filtered and recycled solids component.At 80 ℃ of following drying under reduced pressure, obtain the 24.8g white powder.

The result who analyzes by NMR confirms that do not detect the signal from unsaturated link(age), hydroxyl is present in polymer ends.67% of polymkeric substance one end is a hydroxyl.

[making embodiment 3]

[synthetic end has the poly(lactic acid) (HEMA-PLA) of two keys]

After adding 0.65g (5.0mmol) 2-methacrylic acid hydroxyl ester, 50.4g (350mmol) L-rac-Lactide, 22.0mg (0.22mmol) quinhydrones and 2.5mg (xylene solution that adds 0.5g 0.5wt%) stannous octoate, be reflected in the nitrogen atmosphere and under the condition of 170 ℃/1atm, carried out 4 hours, this postcooling reaction mass.After being dissolved in reaction product in the 250ml chloroform, when stirring, it is precipitated in methyl alcohol, remove remaining L-rac-Lactide by abundant stirring.Carry out suction filtration.Use methyl alcohol to carry out rinsing, under the condition of 60 ℃ and 2kPa dry 24 hours, obtain number-average molecular weight (Mn) and be 9,150 and terminal poly(lactic acid) (HEMA-PLA) 50.1g with two keys.

[making embodiment 4]

[synthetic polyethylene] with the terminal terminal esterification of radical polymerization initiation

To the Dimroth condenser being housed and being packed into 1,700mL dimethylbenzene in the abundant metathetical 2L glass aggregation container by nitrogen.When feeding nitrogen (30L/h), under (600rpm) condition of stirring, temperature is increased to 45 ℃.Next, add 13.1ml triethyl aluminum and 5.4ml vinyl carbinol, and remain on 50 ℃.After 5 minutes, adding is by making metallocene compound 33.7mg shown in the chemical formula (1) for preparing and aluminium trimethide alkane (methyl aluminoxane) (2.22ml toluene solution in the independent 20ml Schrenck bottle with nitrogen replacement, Al concentration is 1.41mol/L) dark green solution that obtains of contact, change nitrogen the ethylene gas of 10L/h into rapidly, the polyreaction low whipping speed is to carry out under 50 ℃ 150 minutes under the condition of 600rpm.After this, add the 20mL isopropylcarbinol and stop polyreaction.Polymeric reaction solution is poured in the methyl alcohol that 2L contains 30ml 1N hydrochloric acid, and stirring is spent the night.Filter with glass filter, the white polymer that obtains 80 ℃ of dry 10 hours of decompressions (1.3kPa) down, is obtained the terminal polyethylene 25.7g that imports vinyl carbinol.The poly weight-average molecular weight of gained (Mw) is 29,500g/mol, and number-average molecular weight (Mn) is 11,200g/mol.The result that NMR analyzes confirms, has 0.92 hydroxyl from vinyl carbinol on each polymer chain.

[Chemical formula 1]

Two mouthfuls of eggplant type flasks of 1L with the polyethylene 20g that contains terminal hydroxy group that above obtains places the degassing and replaces with nitrogen add 400ml dry toluene, 3.9ml triethylamine and 2.8ml 2-bromine isobutyl acylbromide respectively, are heated to 80 ℃, stir 2 hours under heating.Reaction soln is poured in the 2L methyl alcohol into the polymkeric substance that goes out with the glass filter filtering-depositing.In this case, the polymkeric substance on the glass filter used 100ml washed with methanol 3 times successively, use 100ml 1N hydrochloric acid flushing 1 time, use twice of 100ml washed with methanol.With polymkeric substance under the reduced pressure of 50 ℃ and 1.3kPa (10Torr) dry 10 hours. ¹The result that H-NMR analyzes is to have obtained the esterified polymkeric substance of terminal hydroxy group.

[making embodiment 5]

[synthesizing polyethylene-polymethylmethacrylablock block multipolymer (C-2-1)]

Dimroth condenser and stirring rod being housed and adding polymkeric substance 15.0g, 45.3ml methyl methacrylate (MMA) and the 50ml o-Xylol of making the terminal esterification of making among the embodiment 3 in the abundant metathetical 500mL glass reactor, when slowly stirring, be warming up to 80 ℃ with nitrogen.By with 167mg copper (I) bromine, 1.1ml 2M N, N, N ', N "; N "-pentamethyl-diethyl triamine/o-Xylol solution and 5.0ml o-Xylol mix the homogeneous solution that obtains in the Schrenck bottle of nitrogen replacement and import aggregation container independent, temperature is increased to 120 ℃, causes the MMA polymerization when 450rpm stirs.4.5 after hour,, replenish adding 200ml toluene, stirred 1 hour down at 100 ℃ because viscosity increases.After this, pour polymeric reaction solution into 2.0L methyl alcohol, be settled out polymkeric substance.Sedimentary polymkeric substance filters with glass filter, under the reduced pressure of 80 ℃ and 2.0kPa (15Torr) dry 10 hours.

The result that NMR analyzes shows, has obtained having the polyethylene-polymethylmethacrylablock block multipolymer (C-2-1) of 65.3wt% methyl methacrylate polymer.

[making embodiment 6]

[synthesizing polyethylene-polymethylmethacrylablock block multipolymer (C-2-2)]

Dimroth condenser and stirring rod being housed and adding polymkeric substance 77.0g, 86.9ml methyl methacrylate (MMA) and the 324ml o-Xylol of making the terminal esterification of the method synthetic described in the embodiment 3 in the abundant metathetical 500mL glass reactor, when stirring gradually, be warming up to 80 ℃ with nitrogen.By with 855mg copper (I) bromine, 5.4ml 2MN, N, N ', N "; N "-pentamethyl-diethyl triamine/o-Xylol solution and 5.0ml o-Xylol mix the homogeneous solution that obtains in the Schrenck bottle of nitrogen replacement and import aggregation container independent, temperature is increased to 120 ℃, causes the MMA polyreaction when 450rpm stirs.3.5 after hour, replenish adding 200ml toluene, stirred 1 hour down at 100 ℃.After this, pour polymeric reaction solution into 2.0L methyl alcohol, be settled out polymkeric substance.Sedimentary polymkeric substance filters with glass filter, under the reduced pressure of 80 ℃ and 2.0kPa (15Torr) dry 10 hours.The result that NMR analyzes shows, has obtained having the polyethylene-polymethylmethacrylablock block multipolymer (C-2-2) of 39.1wt% methyl methacrylate polymer.

[making embodiment 7]

[synthetic polypropylene] with the terminal terminal esterification of radical polymerization initiation

With 57.4g make the polypropylene that contains terminal hydroxy group that obtains among the embodiment 2 place the degassing, and with two mouthfuls of eggplant type flasks of 1L of nitrogen replacement, add 500ml dry toluene, 4.1ml triethylamine and 3.1ml 2-bromine isobutyl acylbromide respectively, temperature is increased to 80 ℃, heated and stirred 3 hours.

Add 20ml methyl alcohol in the pulpous state reaction mixture after, be cooled to room temperature, polymkeric substance filters with glass filter.In this case, the polymkeric substance on the glass filter is used 100ml washed with methanol 3 times successively, uses 100ml 1N hydrochloric acid flushing 1 time, used 100ml pure water rinsing twice, use twice of 100ml washed with methanol.With polymkeric substance under the reduced pressure of 50 ℃ and 1.3kPa (10Torr) dry 10 hours. ¹The result that H-NMR analyzes is to have obtained the esterified polymkeric substance of terminal hydroxy group.

[making embodiment 8]

[synthetic polypropylene-polymethylmethacrylablock block multipolymer (C-3-1)]

Dimroth condenser and stirring rod are being housed and polypropylene, 30.3ml methyl methacrylate (MMA) and the 98.2ml o-Xylol of the above-mentioned terminal esterification of 28.8g of packing in the abundant metathetical 500mL glass reactor with nitrogen, when stirring gradually, are being warming up to 120 ℃.Will be by with 100mg copper (I) bromine, 0.63ml 2M N, N, N ', N "; N "-pentamethyl-diethyl triamine/o-Xylol solution and 5.0ml o-Xylol mix the homogeneous solution that obtains in the Schrenck bottle of nitrogen replacement and import aggregation container independent, temperature is increased to 120 ℃, causes the MMA polyreaction when 350rpm stirs.7.0 after hour, add 150ml toluene and dilute, add the 20ml isopropylcarbinol, temperature is cooled to room temperature.Pour polymeric reaction solution into 1.5L methyl alcohol, precipitation polymers.Sedimentary polymkeric substance filters with glass filter, and with 20ml washed with methanol twice, drying is 10 hours under the reduced pressure of 80 ℃ and 2.0kPa (15Torr).

The result that NMR analyzes shows, obtained containing about 33wt% unreacted homo-polypropylene, had methyl methacrylate segmental polypropylene-polymethylmethacrylablock block multipolymer (C-3-1) of 36.3wt%.

[making embodiment 9]

[synthetic polypropylene-polymethylmethacrylablock block multipolymer (C-3-2)]

Dimroth condenser and stirring rod being housed and polypropylene, 48.5ml methyl methacrylate (MMA) and the 58.7ml o-Xylol of the terminal esterification that the 17.3g that packs in the abundant metathetical 500mL glass reactor with nitrogen makes with the same procedure of making embodiment 3, be warming up to 120 ℃ in the stirring gradually.Will be by with 60mg copper (I) bromine, 0.38ml 2MN, N, N ', N "; N "-pentamethyl-diethyl triamine/o-Xylol solution and 5.0ml o-Xylol mix the homogeneous solution that obtains in the Schrenck bottle of nitrogen replacement and import aggregation container independent, cause the MMA polyreaction when stirring with 350rpm under 120 ℃.7.0 after hour, add 150ml toluene and dilute, add the 20ml isopropylcarbinol, temperature is cooled to room temperature.Pour polymeric reaction solution into 1.5L methyl alcohol, precipitation polymers.Sedimentary polymkeric substance filters with glass filter, and after twice of 20ml washed with methanol, drying is 10 hours under the reduced pressure of 80 ℃ and 2.0kPa (15Torr).

The result that NMR analyzes shows, obtained containing about 20wt% unreacted homo-polypropylene, had methyl methacrylate segmental polypropylene-polymethylmethacrylablock block multipolymer (C-3-2) of 59.9wt%.

[embodiment 1]

[synthetic HEMA-PP/PLA multipolymer (C-1-1)]

10.0g is made the HEMA-PP and the 40.0g that obtain among the embodiment 1 when feeding nitrogen, in the separable flask of 100ml, under the condition of 130 ℃/100kPa (1atm), stir dissolving HEMA-PP in advance with the xylol of molecular sieve 3a dehydration.After the cooling, add 10.0g rac-Lactide and 0.005g stannous octoate (adding 1.0g 0.5wt% xylene solution), be reflected under the condition of 130 ℃/100kPa (1atm) and in nitrogen atmosphere, carried out 4 hours.After reaction is finished, add the xylol of 50g dehydration, stir, cool off gradually then, thereby make polymer crystallization until evenly.Crystalline material is joined in the 400g methyl alcohol, after fully stirring, carry out suction filtration.Filter cake is joined in the 400g methyl alcohol once more, after the stirring, carry out suction filtration.In the suction filtration process, other 400g methyl alcohol is divided into several parts pours flush cake into from the top.After reclaiming filter cake, that it is following dry 24 hours at 80 ℃ in blast dryer.The weight of resulting polymers is 18.8g.

[embodiment 2]

[synthetic HEMA-PP/PLA multipolymer (C-1-2)]

10.0g is made the HEMA-PP and the 40.0g that obtain among the embodiment 1 when feeding nitrogen, in the separable flask of 100ml, under the condition of 130 ℃/100kPa (1atm), stir dissolving HEMA-PP in advance with the xylol of molecular sieve 3a dehydration.After the cooling, add 30.0g rac-Lactide and 0.015g stannous octoate (adding 3.0g 0.5wt% xylene solution), be reflected under the condition of 130 ℃/100kPa (1atm) and in nitrogen atmosphere, carried out 4 hours.After reaction is finished, add the xylol of 50g dehydration, stir, cool off gradually then, thereby make polymer crystallization until evenly.Crystalline material is joined in the 400g methyl alcohol, after fully stirring, carry out suction filtration.Filter cake is joined in the 400g methyl alcohol once more, after the stirring, carry out suction filtration.In the suction filtration process, other 400g methyl alcohol is divided into several parts pours flush cake into from the top.After reclaiming filter cake, that it is following dry 24 hours at 80 ℃ in blast dryer.The weight of resulting polymers is 34.0g.

[embodiment 3]

[synthetic HEMA-PP/PLA multipolymer (C-1-3)]

10.0g is made the HEMA-PP and the 60.0g that obtain among the embodiment 1 when feeding nitrogen, in the separable flask of 200ml, under the condition of 130 ℃/100kPa (1atm), stir dissolving HEMA-PP in advance with the xylol of molecular sieve 3a dehydration.After the cooling, add 50.0g rac-Lactide and 0.025g stannous octoate (adding 5.0g 0.5wt% xylene solution), be reflected under the condition of 130 ℃/100kPa (1atm) and in nitrogen atmosphere, carried out 4 hours.After reaction is finished, add the xylol of 70g dehydration, stir, cool off gradually then, thereby make polymer crystallization until evenly.Crystalline material is joined in the 500g methyl alcohol, after fully stirring, carry out suction filtration.Filter cake is joined in the 500g methyl alcohol once more, after the stirring, carry out suction filtration.In the suction filtration process, other 500g methyl alcohol is divided into several parts pours flush cake into from the top.After reclaiming filter cake, that it is following dry 24 hours at 80 ℃ in blast dryer.The weight of resulting polymers is 53.8g.

[embodiment 4]

[synthetic HEMA-PP/PLA multipolymer (C-1-4)]

36.0g is made HEMA-PLA, the 36.0g melt flow rate (MFR) (MFR that obtains among the embodiment 3; 230 ℃, 2160g) for 0.02g/10min, in 135 ℃ of perhydronaphthalenes, record intrinsic viscosity [η] for 10.5dl/g, accumulation pore volume be the alfon powder of 0.25cc/g and 0.72g t-butyl per(oxy)benzoate (PBZ:NOF Corporation product) with laboplast mill melting mixing under the condition of 190 ℃ of temperature, 5 minutes time and revolution 50rpm that Toyo SeikiCo. makes, obtain HEMA-PP/PLA multipolymer (C-1-4).The number-average molecular weight (Mn) that this multipolymer (C-1-4) records by GPC is 27,000.

[embodiment 5]

[synthetic PP-OH/PLA multipolymer (C-1-5)]

20.0g is made the PP-OH and the 80.0g that obtain among the embodiment 2 when feeding nitrogen, in the separable flask of 200ml, under the condition of 130 ℃/100kPa (1atm), stir dissolving PP-OH in advance with the xylol of molecular sieve 3a dehydration.After the cooling, add 8.0g rac-Lactide and 0.004g stannous octoate (adding 0.8g 0.5wt% xylene solution), be reflected under the condition of 130 ℃/100kPa (1atm) and in nitrogen atmosphere, carried out 4 hours.After reaction is finished, add the xylol of 80g dehydration, stir, cool off gradually then, thereby make polymer crystallization until evenly.Crystalline material is joined in the 600g methyl alcohol, after fully stirring, carry out suction filtration.Filter cake is joined in the 600g methyl alcohol once more, after the stirring, carry out suction filtration.In the suction filtration process, other 600g methyl alcohol is divided into several parts pours flush cake into from the top.After reclaiming filter cake, that it is following dry 24 hours at 80 ℃ in blast dryer.The weight of resulting polymers is 26.4g.

[embodiment 6]

[synthetic PP-OH/PLA multipolymer (C-1-6)]

10.0g is made the PP-OH and the 40.0g that obtain among the embodiment 2 when feeding nitrogen, in the separable flask of 100ml, under the condition of 130 ℃/100kPa (1atm), stir dissolving PP-OH in advance with the xylol of molecular sieve 3a dehydration.After the cooling, add 10.0g rac-Lactide and 0.005g stannous octoate (adding 1.0g 0.5wt% xylene solution), be reflected under the condition of 130 ℃/100kPa (1atm) and in nitrogen atmosphere, carried out 4 hours.After reaction is finished, add the xylol of 50g dehydration, stir, cool off gradually then, thereby make polymer crystallization until evenly.Crystalline material is joined in the 400g methyl alcohol, after fully stirring, carry out suction filtration.Filter cake is joined in the 400g methyl alcohol once more, after the stirring, carry out suction filtration.In the suction filtration process, other 400g methyl alcohol is divided into several parts pours flush cake into from the top.After reclaiming filter cake, that it is following dry 24 hours at 80 ℃ in blast dryer.The weight of resulting polymers is 18.4g.

[embodiment 7]

[synthetic PP-OH/PLA multipolymer (C-1-7)]

10.0g is made the PP-OH and the 40.0g that obtain among the embodiment 2 when feeding nitrogen, in the separable flask of 100ml, under the condition of 130 ℃/100kPa (1atm), stir dissolving PP-OH in advance with the xylol of molecular sieve 3a dehydration.After the cooling, add 20.0g rac-Lactide and 0.010g stannous octoate (adding 2.0g 0.5wt% xylene solution), be reflected under the condition of 130 ℃/100kPa (1atm) and in nitrogen atmosphere, carried out 4 hours.After reaction is finished, add the xylol of 50g dehydration, stir, cool off gradually then, thereby make polymer crystallization until evenly.Crystalline material is joined in the 400g methyl alcohol, after fully stirring, carry out suction filtration.Filter cake is joined in the 400g methyl alcohol once more, after the stirring, carry out suction filtration.In the suction filtration process, other 400g methyl alcohol is divided into several parts pours flush cake into from the top.After reclaiming filter cake, that it is following dry 24 hours at 80 ℃ in blast dryer.The weight of resulting polymers is 27.9g.

[embodiment 8]

With 50 weight part Mitsui Chemicals, homo-polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; MFR:24.9g/10min under 230 ℃, fusing point: 161 ℃, weight-average molecular weight: 222,000), 50 weight part Mitsui Chemicals, the multipolymer (C-1-1) that obtains among poly(lactic acid) (registrar entitling LACEA Grade H100) that Inc. makes and the 5 weight part embodiment 1 carries out melting mixing with the Laboplast mill of Toyo Seiki Kogyo Co. manufacturing under the condition of 200 ℃ of temperature, 5 minutes time, revolution 100rpm.The resin combination of gained (D-1) outward appearance is even.Take out a part and use its cross section of transmission electron microscope observation.The result is, poly(lactic acid) is the island phase mutually, and polypropylene is marine facies (sea phase).The size of island phase is about about 5 μ m or littler.

[comparing embodiment 1]

With 50 weight part Mitsui Chemicals, polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; MFR:24.9g/10min under 230 ℃, weight-average molecular weight: 222,000) and 50 weight part Mitsui Chemicals, Inc. the poly(lactic acid) of Zhi Zaoing (registrar entitling LACEA Grade H100) is with the mode melting mixing identical with embodiment 8, and its difference is not use multipolymer (C-1-1).Result with observation by light microscope section is, poly(lactic acid) is the island phase mutually, and polypropylene is marine facies.The size of island phase is about about 20 μ m or bigger.

[embodiment 9]

Polyolefin resin/polylactic acid based resin combination (D-1) that embodiment 8 is obtained is at 200 ℃ of temperature, pressure 10MPa (100kg/cm ²), carry out pressure forming under the conditions of 5 minutes clamping times, obtain the square compressing tablet of thick 1mm, length of side 40mm.The gained compressing tablet is cut into the square of 5mm * 5mm, obtains testing plate.Carry out the thermotolerance test according to the described method of JIS K7196.Particularly, use TMA5200 (Seiko Instruments Inc. product), use the pressure head of diameter 1mm to impose 50gf/cm ²Load, under the intensification condition of 2 ℃/min, under nitrogen gas stream, test, read the infiltration temperature, this temperature is as texturing temperature.The softening temperature of this testing plate is 70 ℃.

[comparing embodiment 2]

With itsui Chemicals, the poly(lactic acid) (registrar entitling LACEA GradeH100) that Inc. makes is carried out molding in the mode identical with embodiment 9, and the measuring result of softening temperature is 55 ℃.

[comparing embodiment 3]

Will by with 15 weight part syndiotactic polypropylenes (weight-average molecular weight 250,000) and poly(lactic acid) (Mitsui Chemicals, Inc. makes; Registrar entitling LACEA, Grade H100) resin combination that obtains of melting mixing carries out molding in the mode identical with embodiment 9, and the measuring result of softening temperature is 57 ℃.

[embodiment 10]

With 85wt% is poly(lactic acid) (the registrar entitling LACEA of the Mitsui Chemicals manufacturing of 89.5 weight parts, Grade H100), 10wt% is the Mitsui Chemicals of 10.5 weight parts, Inc. the ethylene-butylene copolymer of Zhi Zaoing (registrar entitling TAFMER, Grade A4050) and 5wt% promptly the polyethylene of 5.3 weight parts-polymethylmethacrylablock block multipolymer (C-2-1) mix, the Laboplast mill with Toyo SeikiKogyo Co. manufacturing under the condition of 200 ℃ of temperature, 5 minutes time, revolution 100rpm mediates.The resin combination that obtains is heated under 200 ℃ temperature, at pressure 10MPa (100kg/cm ²), carry out pressure forming under the conditions of 5 minutes clamping times, quench then, obtain the moulded product of thick 3mm, wide 6mm and long 12.6mm.Go up the formation breach at the moulded product (E-2) of gained.The Izod shock strength that records according to ASTMD256 is 378J/m, and it is half fracture.

[embodiment 11]

Mix and moulding in the mode identical with embodiment 10, obtain moulded product (D-3), its difference is to use i.e. poly(lactic acid) (the registrar entitling LACEA of the Mitsui Chemicals manufacturing of 89.5 weight parts of 85wt%, Grade H100), 10wt% is the Mitsui Chemicals of 10.5 weight parts, Inc. ethylene-butylene copolymer of Zhi Zaoing (registrar entitling TAFMER, Grade A4050) and 5wt% are the above-mentioned polyethylene-polymethylmethacrylablock block multipolymer (C-2-2) of 5.3 weight parts.The Izod shock strength (23 ℃, breach) that records moulded product (D-3) according to ASTMD256 is 382J/m, and it is half fracture.

[comparing embodiment]

Carry out fusion and moulding in the mode identical with embodiment 11, obtain moulded product, its difference is the poly(lactic acid) (registrar entitling LACEA, Grade H100) of using 100 weight part Mitsui Chemicals to make.On the moulded product of gained, form breach.The Izod shock strength (23 ℃, breach) that records according to ASTMD256 is 33J/m.

[comparing embodiment 5]

Carry out fusion and moulding in the mode identical with embodiment 11, obtain moulded product, its difference is to use poly(lactic acid) (the registrar entitling LACEA of 85 weight part Mitsui Chemicals manufacturing, Grade H100) and 15 weight part Mitsui Chemicals, Inc. the ethylene-butylene copolymer of Zhi Zaoing (registrar entitling TAFMER, Grade A4050).On the moulded product of gained, form breach.The Izod shock strength (23 ℃, breach) that records according to ASTMD256 is 39J/m.

[embodiment 12]

With 50 weight part Mitsui Chemicals, poly(lactic acid) (registrar entitling LACEAGrade H100), 50 weight part Mitsui Chemicals that Inc. makes, polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; MFR:24.9g/10min under 230 ℃, fusing point: 161 ℃, weight-average molecular weight: 222,000) and the above-mentioned polypropylene of 5 weight parts-polymethylmethacrylablock block multipolymer (C-3-1) mixes, and mediates under the condition of 200 ℃ of temperature, 5 minutes time, revolution 100rpm with the Laboplast mill of Toyo Seiki Kogyo Co. manufacturing.The resin combination outward appearance of gained is even.Take out a part and use its cross section of transmission electron microscope observation.The result is, poly(lactic acid) is the island phase mutually, and polypropylene is marine facies.The size of island phase is about 5 μ m or littler.

With the above-mentioned resin combination that obtains (D-1) at 200 ℃ of temperature, pressure 10MPa (100kg/cm ²), carry out pressure forming under the conditions of 5 minutes clamping times, obtain the square compressing tablet of thick 1mm, length of side 40mm.The gained compressing tablet is cut into the square of 5mm * 5mm, obtains testing plate.Carry out the thermotolerance test according to the described method of JIS K7196.Particularly, use TMA5200 (Seiko Instruments Inc. product), use the pressure head of diameter 1mm to impose 50gf/cm ²Load, under the intensification condition of 2 ℃/min, under nitrogen gas stream, test, read the infiltration temperature, this temperature is as texturing temperature.The softening temperature of this testing plate is 72 ℃.

[embodiment 13]

It is even to mix the resin combination outward appearance that obtains in the mode identical with embodiment 12, its difference is to use 50 weight part Mitsui Chemicals, Inc. the poly(lactic acid) of Zhi Zaoing (registrar entitling LACEA Grade H100), 50 weight part Mitsui Chemicals, polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; MFR:24.9g/10min under 230 ℃, fusing point: 161 ℃, 222,000) and the above-mentioned polypropylene of 5 weight parts-polymethylmethacrylablock block multipolymer (C-3-2) weight-average molecular weight:.Take out a part and use its cross section of transmission electron microscope observation.The result is, poly(lactic acid) is the island phase mutually, and polypropylene is marine facies.The size of island phase is about 5 μ m or littler.

Use the above-mentioned branch composition that obtains, measure softening temperature in the mode identical with embodiment 9 according to the described method of JIS K7196.The softening temperature of this testing plate is 67 ℃.

[embodiment 14]

With 50 weight part Mitsui Chemicals, poly(lactic acid) (registrar entitling LACEA Grade H100), 50 weight part Mitsui Chemicals that Inc. makes, polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; MFR:24.9g/10min under 230 ℃, fusing point: 161 ℃, 222,000), the above-mentioned multipolymer of 5 weight parts (C-3-1), 10 weight parts be as talcum (the Fuji Talc Kogyo Co. product of mineral filler weight-average molecular weight:; Median size: 4.2 μ m, apparent density; 0.13g/ml, whiteness; 98.5%) and 10 weight parts as the styrene-ethylene-butylene-styrene of the rubber series SEBS rubber (MFR:4.5g/10min that records under 230 ℃, proportion: 0.89, styrene content: 18wt%) carry out uniform mixing with mixing machine, use twin-screw extruder TEM35BS (Toshiba Machine Co. product) melt kneading under 180 ℃ barrel temperature, granulation then obtains thermoplastic resin composition (D).Next, with injector Ti-80G2 (Toyo Machinery ﹠amp; Metal Co., Ltd. product) under the condition of 170 to 200 ℃ of default barrel temperatures, 80 ℃ of molding temperatures, injection and 10 seconds residence times, 30 seconds cooling times, it is carried out injection-moldedly, obtain the thick ASTM testing plate of 3.2mm.Gained testing plate heat-drawn wire under the load of 0.45MPa is 63 ℃, and the Izod shock strength under 23 ℃ of atmosphere is 101J/m.Further, the particle of melt kneading is carried out molding, measure softening temperature according to the method described in the JIS K7196 in the mode identical with embodiment 9.The softening temperature of this testing plate is 167.3 ℃.

[embodiment 15]

With 50 weight part Mitsui Chemicals, poly(lactic acid) (registrar entitling LACEA Grade H100), 50 weight part Mitsui Chemicals that Inc. makes, block polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; MFR:25g/10min under 230 ℃, proportion: 0.91,8%), 10 weight part SEBS (AsahiKasei Corporation product, TUFTEC be dissolved in the one-tenth component in the standard perhydronaphthalene:; 230 ℃ of temperature, load 2.16kgf MFR:4.5g/10min down, styrene/ethylene-butylene compares: 18/82,0.89), 10 weight part talcums (Fuji Talc Kogyo Co. product proportion:; Median size: 4.2 μ m, apparent density; 0.13g/ml, whiteness; 98.5%) and the above-mentioned multipolymer of 5 weight parts (C-1-3) carry out uniform mixing with mixing machine, use twin-screw extruder TEM35BS (Toshiba Machine Co. product) melt kneading under 180 ℃ barrel temperature, granulation then obtains thermoplastic resin composition (D).Next; under the condition of 210 ℃ of default barrel temperatures, 80 ℃ of molding temperatures, injection and 10 seconds residence times, 30 seconds cooling times, it is carried out injection-moldedly with injector IS-55 (Toshiba Machine Co. product), obtain the thick ASTM testing plate of 3.2mm.Gained testing plate heat-drawn wire under the load of 0.45MPa is 77 ℃, and the Izod shock strength under 23 ℃ of atmosphere is 110J/m.Further, the particle of melt kneading is carried out molding, measure softening temperature according to the method described in the JIS K7196 in the mode identical with embodiment 9.The softening temperature of this testing plate is 164.9 ℃.

[embodiment 16]

With 50 weight part Mitsui Chemicals, poly(lactic acid) (registrar entitling LACEA Grade H100), 50 weight part Mitsui Chemicals that Inc. makes, polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; The MFR:13g/10min that records under 230 ℃, fusing point: 165 ℃, 339,000), the above-mentioned multipolymer of 5 weight parts (C-1-3), 10 weight parts be as talcum (the Fuji Talc Kogyo Co. product of mineral filler weight-average molecular weight:; Median size: 4.2 μ m, apparent density; 0.13g/ml, whiteness; 98.5%) and 10 weight parts as the styrene-ethylene-butylene-styrene of the rubber series SEBS rubber (MFR:4.5g/10min that records under 230 ℃, proportion: 0.89, styrene content: 18wt%) carry out uniform mixing with mixing machine, use twin-screw extruder TEM35BS (Toshiba Machine Co. product) melt kneading under 180 ℃ barrel temperature, granulation then obtains thermoplastic resin composition (D).Next, with injector Ti-80G2 (Toyo Machinery ﹠amp; Metal Co., Ltd. product) under the condition of 170 to 200 ℃ of default barrel temperatures, 80 ℃ of molding temperatures, injection and 10 seconds residence times, 30 seconds cooling times, it is carried out injection-moldedly, obtain the thick ASTM testing plate of 3.2mm.The heat-drawn wire of gained testing plate under the load of 0.45MPa is 105 ℃, and the Izod shock strength under 23 ℃ of atmosphere is 103J/m.Further, the particle of melt kneading is carried out molding, measure softening temperature according to the method described in the JIS K7196 in the mode identical with embodiment 9.The softening temperature of this testing plate is 167.4 ℃.

[comparing embodiment 6]

Similar to embodiment 16, its difference is not add multipolymer (C-1-3), with 50 weight part Mitsui Chemicals, Inc. the poly(lactic acid) of Zhi Zaoing (registrar entitling LACEA GradeH100), 50 weight part Mitsui Chemicals, block polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; The MFR:25g/10min that records under 230 ℃, proportion: 0.91,8%), 10 weight part SEBS (Asahi KaseiCorporation product, TUFTEC be dissolved in the one-tenth component in the standard perhydronaphthalene:; 230 ℃ of temperature, load 2.16kgf MFR:4.5g/10min down, styrene/ethylene-butylene compares: 18/82,0.89), 10 weight part talcums (C-1) (Fuji Talc Kogyo Co. product proportion:; Median size: 4.2 μ m, apparent density; 0.13g/ml, whiteness; 98.5%) carry out uniform mixing with mixing machine, use twin-screw extruder TEM35BS (Toshiba Machine Co. product) melt kneading under 200 ℃ barrel temperature, granulation then obtains thermoplastic resin composition (D).Next; under the condition of 170 to 210 ℃ of default barrel temperatures, 30 ℃ of molding temperatures, injection and 10 seconds residence times, 30 seconds cooling times, it is carried out injection-moldedly with injector IS-55 (ToshibaMachine Co. product), obtain the thick ASTM testing plate of 3.2mm.The heat-drawn wire of gained testing plate under the load of 0.45MPa is 58 ℃, and the Izod shock strength under 23 ℃ of atmosphere is 55J/m.Owing to do not add modified polyolefin, shock strength reduces.Further, the particle of melt kneading is carried out molding, measure softening temperature according to the method described in the JIS K7196 in the mode identical with embodiment 9.The softening temperature of this testing plate is 58.6 ℃.

[embodiment 17]

With poly(lactic acid) (registrar entitling LACEA, Grade H280), the 50 weight part Mitsui Chemicals that the Mitsui Chemicals of 50wt% makes, block polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; The MFR:25g/10min that records under 230 ℃, proportion: 0.91, be dissolved in the one-tenth component in the standard perhydronaphthalene: 8%) and the above-mentioned multipolymer of 5 weight parts (C-1-3) mix, the Laboplast mill that makes with Toyo Seiki Kogyo Co. under the condition of 200 ℃ of temperature, 5 minutes time, revolution 100rpm mediates, at pressure 1.0MPa (100kg/cm ²), carry out pressure forming under the conditions of 5 minutes clamping times, quench then, obtain faint yellow-white translucent sheet material.After this, by in 120 ℃ of lower edge single shaft directions with the area of 4 times or more times than strong pull, obtain white smooth film.The result of sem observation shows that the cavity that poly(lactic acid) and polypropylene are peeled off is less than 10 μ m on the interface, this film is enough to as the reflecting material film.

[comparing embodiment 7]

Similar to embodiment 17, its difference is not add multipolymer (C-1-3), poly(lactic acid) (the registrar entitling LACEA that the Mitsui Chemicals of 50wt% is made, GradeH280), 50 weight part Mitsui Chemicals, block polypropylene (the registrar entitling MITSUI POLYPRO that Inc. makes; The MFR:25g/10min that records under 230 ℃, proportion: 0.91, be dissolved in the one-tenth component in the standard perhydronaphthalene: 8%) and 5 weight part multipolymers (C-1-3) mix, the Laboplast mill that makes with Toyo Seiki KogyoCo. under the condition of 200 ℃ of temperature, 5 minutes time, revolution 100rpm mediates, at pressure 10MPa (100kg/cm ²), carry out pressure forming under the conditions of 5 minutes clamping times, quench then, obtain faint yellow-white translucent sheet material.After this, when under 120 ℃ with its along the single shaft direction with the area of 4 times or more times during than strong pull, the film that obtains is rough.The result of sem observation shows that the cavity that poly(lactic acid) and polypropylene are peeled off has surpassed 50 μ m on the interface, this film is not enough to as the reflecting material film.

Industrial applicability

By according to of the present invention contain aliphatic polyester resin (A), vistanex (B) and The mechanograph that the resin combination (D) of modified polyolefin resin (C) obtains is in heat resistance and anti-The impact aspect is very excellent, and it can be used as automotive material, home electric appliance material parts, electricity Gas and electronic unit, container, medical material and other multiple industrial materials.

Claims (13)

1. a resin combination (D) is characterized in that containing the aliphatic polyester resin (A) of 1 to 99 weight part, the polyolefin resin (B) of 99 to 1 weight parts (condition is 100 weight parts for (A) and summation (B)) and is the modified polyolefin resin (C) of 0.1 to 100 weight part of 100 weight parts based on (A) and summation (B).

2. resin combination (D), it is characterized in that described modified polyolefin resin (C) amount be being selected from of 0.1 to 100 weight part (C-1), (C-2) and (C-3) at least a:

(C-1) multipolymer, it has following structure: propenyl polyolefine segment, (a) and contain the segment of lactic acid as integral part, (b) by covalent linkage with block state and/or the combination of grafting shape, propenyl polyolefine segment wherein, (b) number-average molecular weight is 1,000 to 100,000, contain the segment of lactic acid as integral part, (a) number-average molecular weight is 1,000 to 200,000, propenyl polyolefine segment, (a) and contain the segment of lactic acid as integral part, (b) weight consists of 10/90 to 90/10

(C-2) multipolymer, it has following structure: contain the acrylic acid series unit as the segment of integral part and vinyl polyolefine segment by covalent linkage with block state and/or grafting state and/or disorganized form combination and

(C-3) multipolymer, it has following structure: contain the acrylic acid series unit as the segment of integral part and propenyl polyolefine segment by covalent linkage with block state and/or grafting state and/or disorganized form combination.

3. a modified polyolefin resin (C-1), it comprises the multipolymer with following structure: propenyl polyolefine segment (a) and contain lactic acid as the segment (b) of integral part by covalent linkage with block state and/or grafting combinations of states, wherein the number-average molecular weight of propenyl polyolefine segment (b) is 1,000 to 100,000, containing lactic acid is 1 as the number-average molecular weight of the segment (a) of integral part, 000 to 200,000, propenyl polyolefine segment (a) and contain lactic acid and consist of 10/90 to 90/10 as the weight of the end of the chain (b) of integral part.

4. according to the manufacture method of the modified polyolefin resin (C-1) of claim 1-3, it is characterized in that to contain monomer and polyolefin resin polymerization in the presence of modified polyolefin resin of rac-Lactide or lactic acid, wherein said modified polyolefin resin has the grafting vinyl monomer that contains hydroxyl thereon, perhaps vinyl monomer and polymer of monomers that contains rac-Lactide or lactic acid and polyolefine reaction.

5. according to the resin combination (D) of claim 2, wherein said modified polyolefin resin (C-2) is to have to contain acrylic acid units as the segment of integral part and the multipolymer of vinyl polyolefin block.

6. according to the resin combination (D) of claim 2, wherein said modified polyolefin resin (C-2) is to have to contain methyl methacrylate units as the segment of integral part and the multipolymer of vinyl polyolefin block.

7. according to the resin combination (D) of claim 2, wherein said modified polyolefin resin (C-3) is to have to contain acrylic acid units as the segment of integral part and the multipolymer of propenyl polyolefin block.

8. according to the resin combination (D) of claim 2, wherein said modified polyolefin resin (C-3) is to have to contain methyl methacrylate units as the segment of integral part and the multipolymer of propenyl polyolefin block.

9. a resin combination (D), it is characterized in that it is obtained by the resin combination that contains following component: the polyolefin resin (B) of the aliphatic polyester resin of 40 to 99 weight parts (A), 60 to 1 weight parts (condition is 100 weight parts for (A) and summation (B)) and as modified polyolefin resin (C) based on (A) and summation (B) be being selected from of 0.1 to 50 weight part (C-1), (C-2) of 100 weight parts and (C-3) at least a, and its softening temperature is 60 ℃ or higher.

10. a resin combination (D), it is characterized in that it is obtained by the resin combination that contains following component: the polyolefin resin (B) of the aliphatic polyester resin of 40 to 99 weight parts (A), 60 to 1 weight parts (condition is 100 weight parts for (A) and summation (B)) and as modified polyolefin resin (C) based on (A) and summation (B) be being selected from of 0.1 to 50 weight part (C-1), (C-2) of 100 weight parts and (C-3) at least a, and its Izod shock strength is 100J/m or higher.

11. automotive material parts that comprise the resin combination according to claim 1 (D).

12. home electric appliance material parts that comprises the resin combination according to claim 1 (D).

13. electrical/electronic material components that comprises the resin combination according to claim 1 (D).