CN101631821A - Aliphatic polyester sheet and by its formed body that forms - Google Patents

Abstract

Aliphatic polyester sheet of the present invention has degree of crystallinity χ at least _ABe 3～60% the layer A that comprises aliphatic polyester, and whole mist degree is below 10%.The invention provides the excellent aliphatic polyester sheet of formability, thermotolerance, shock resistance, the transparency and by its formed body that forms.

Description

Aliphatic polyester sheet and by its formed body that forms

Technical field

The present invention relates to have thermotolerance, the aliphatic polyester sheet of shock resistance, the transparency, formability, and formed body.

Background technology

In recent years, because Environmental awareness improves, the greenhouse effects of the earth problem that the discarded soil pollution problem that causes of plastics and the burning that results from cause carbonic acid gas to increase receives publicity.As countermeasure, big quantity research, various Biodegradable resins have been developed, as countermeasure, even big quantity research, developed and burned the resin of forming also for the raw material that brings new carbonic acid gas load in the atmosphere by from plant at the latter at the former.Even for container classes such as the conformal utensil class of using in using at the demonstration package of extensive stock etc., food disc, beverage cups, the goods of the resin that also developed various use Biodegradable resins, forms by raw material from plant.Wherein particularly as the poly(lactic acid) of aliphatic polyester, as biological degradation, from the plastics of plant since second-order transition temperature up to about 60 ℃ and transparent etc., therefore the most noticeable as material with futurity.

Yet poly(lactic acid) is compared with existing raw material from oil, for example polyethylene terephthalate, and if use, there are problems such as thermotolerance deficiency in low 20 ℃ approximately of second-order transition temperatures in each existing purposes.

As the method that is used to address this problem, the someone has proposed to make the poly(lactic acid) crystallization, thereby improves stable on heating technology.

For example, patent documentation 1 has been put down in writing the poly (lactic acid) composition that will contain transparent nucleater and has been heat-treated when moulding or after the moulding, thereby improves crystalline technology.Present technique is given thermotolerance because crystallization is carried out in forming mould thermal treatment during by moulding or the thermal treatment after the moulding, so the thermotolerance deficiency of sheet itself.

Patent documentation 2 has been put down in writing by its stretch orientation is heat-treated or made to the sheet before the moulding, thus the technology of the heating mould release property when giving moulding.But the transparency of sheet and moulding product is very insufficient in the present technique.

In addition, patent documentation 3 has been put down in writing and has been passed through crystalline polylactic acid is mixed with non-crystalline poly(lactic acid), thus the technology of giving the drawing sheet hot formability.But in the present technique,, therefore can not give sufficient thermotolerance owing to the amorphism poly(lactic acid) that contains more than 50%.

Patent documentation 4 has proposed to have the big poly lactic acid series sheet of folding strength of following chip architecture, and described structure is that internal layer is poly(lactic acid) and lactic acid series polyester, outer for containing the 2 kinds 3 layers such chip architecture of poly(lactic acid) of transparent nucleater.Thermal treatment yet technology disclosed herein exists during moulding and the problem of transparent variation.

That patent documentation 5 has proposed to make is variant by the D body burden of polylactic resin, be the discrepant 2 layers of lamination sheet thermal crystallization that constitutes of crystallinity, thereby have formability and stable on heating technology concurrently, but the transparency is very insufficient in the present technique content.

Patent documentation 1: the spy opens flat 9-278991 communique

Patent documentation 2: the spy opens the 2003-245971 communique

Patent documentation 3: the spy opens the 2004-204128 communique

Patent documentation 4: the spy opens the 2005-119062 communique

Patent documentation 5: the spy opens the 2005-125765 communique

Summary of the invention

The present invention is in view of described background, and purpose provides the aliphatic polyester sheet and the formed body thereof of thermotolerance, shock resistance, the transparency, formability excellence.

In order to solve above-mentioned problem, aliphatic polyester sheet of the present invention and adopt following method by its formed body that forms.

(1) a kind of aliphatic polyester sheet has the layer A that comprises aliphatic polyester, the degree of crystallinity χ of this layer A at least _ABe 3～60%, the compound that this layer A contains crystallization nucleating agent and have hydrogen bonded with crystallization nucleating agent, whole mist degree are below 10%.

(2) according to above-mentioned (1) described aliphatic polyester sheet, it is characterized in that, described comprise aliphatic polyester the layer A in, as crystallization nucleating agent, contain at least a kind that is selected from aliphatics carboxylic acid amides and the N-replacement urea, and the compound as having hydrogen bonded with crystallization nucleating agent contains at least a kind that is selected from aliphatics alcohols, Sorbitol Powder based compound, amino acid and the polypeptide.

(3) according to above-mentioned (1) described aliphatic polyester sheet, it is characterized in that described aliphatic polyester is a poly(lactic acid).

(4) according to above-mentioned (1) described aliphatic polyester sheet, it is characterized in that having the layer B that comprises aliphatic polyester at least, the degree of crystallinity χ of layer B _BSatisfy following relational expression, χ _A＞χ _B

According to above-mentioned (3) described aliphatic polyester sheet, it is characterized in that (5) described poly(lactic acid) is by poly (l-lactic acid), form with the mixture of poly-D-lactic acid.

(6) according to above-mentioned (4) described aliphatic polyester sheet, the aliphatic polyester of described layer A and layer B is a poly(lactic acid), constitute containing proportional Da (mole %), satisfying following relational expression, Da＜Db of D-lactic acid units in the poly (l-lactic acid) of described layer A with the proportional Db (mole %) that contains of D-lactic acid units in the poly (l-lactic acid) that constitutes described layer B.

(7) according to above-mentioned (1) described aliphatic polyester sheet, a direction in the face of sheet at 70 ℃ of stress F during 100% elongation down at least ₁₀₀Be 1～10MPa.

According to above-mentioned (5) described aliphatic polyester sheet, it is characterized in that (8) to become component be below the 0.3 quality % to contained lactic acid oligomer in the sheet.

According to above-mentioned (1) described aliphatic polyester sheet, it is characterized in that (9) crystalline size of described layer A is below the 500nm.

According to above-mentioned (4) described aliphatic polyester sheet, it is characterized in that (10) crystalline size of described layer B is below the 500nm.

(11) a kind of formed body is made of above-mentioned (1) described aliphatic polyester sheet.

The thermotolerance of aliphatic polyester sheet of the present invention, shock resistance, formability, transparent good, and, can obtain the formed body of thermotolerance, shock resistance, transparency excellence by using aliphatic polyester sheet.Aliphatic polyester sheet of the present invention is preferably in various blister plastic packagings conformal utensil classes such as (blister packing), container classes such as the food disc of requirement thermotolerance, the transparency, beverage cup, the displaying that requires stable on heating Drink dispenser is with formed body purposes such as bottle, jars, and Industrial materials purposes such as surfacing, laminating material, use in electronic units such as the carrier band carrying purposes etc.

Embodiment

Present inventors are for above-mentioned problem, promptly, the aliphatic polyester sheet and the formed body thereof of thermotolerance, shock resistance, the transparency, formability excellence, further investigate, found that, if the compound that contains crystallization nucleating agent and have hydrogen bonded with crystallization nucleating agent, and degree of crystallinity and whole mist degree is controlled in the specified range, then can solve this problem at one stroke.

To aliphatic polyester sheet of the present invention, importantly: have the layer A that comprises aliphatic polyester at least, the degree of crystallinity χ of this layer A _ABe 3～60%, the compound that this layer A contains crystallization nucleating agent and have hydrogen bonded with crystallization nucleating agent, whole mist degree are below 10%.In addition, aliphatic polyester sheet of the present invention then both can be the single-layer sheet that only is made of layer A as long as have above-mentioned layer A at least, also can be 2 layers, 3 layers lamination sheet with other layer, not restriction especially.

The degree of crystallinity χ that comprises the layer A of aliphatic polyester _APreferable range be 4～50%, more preferably scope is 5～40%.Degree of crystallinity χ at the layer A that comprises aliphatic polyester _AUnder the situation of less than 3%, thermotolerance is insufficient sometimes.In addition, at degree of crystallinity χ _AUnder 60% the situation of surpassing, formability worsens sometimes.

In addition, to aliphatic polyester sheet of the present invention, whole mist degree is to be important below 10%, and preferred whole mist degree is below 8%.More preferably whole mist degree is below 5%, and then is preferably below 3%.If whole mist degree surpasses 10%, then thermotolerance, shock resistance, the transparency, formability worsen sometimes.In addition, as the lower limit of whole mist degree, not restriction especially, the smaller the better, but owing to be difficult to make it less than 0.1% with present technology, so it is generally acknowledged that about 0.1% is lower limit, as long as be 0.5%～10% in addition, then has sufficient characteristic as aliphatic polyester sheet of the present invention.So-called mist degree among the present invention in addition is the conversion haze value when being converted into the sheet of thickness 0.4mm, is to pass through H _0.4(%)=H * 0.4/d (H _0.4: 0.4mm thickness conversion haze value (%), H: the measured value of the mist degree of sheet sample (%), d: the conversion haze value that obtains of the defined formula sheet thickness of sample (mm) of mist degree determination part).In the present invention, this conversion haze value is to be important (as mentioned above, the so-called mist degree of the present invention, short of special narration just means the conversion haze value when being converted into the sheet of thickness 0.4mm by above-mentioned formula) below 10%.

In order to realize thermotolerance, shock resistance, formability, the transparency whole, be to be very important key aspect following (1)～(4) below 10% with whole mist degree inhibition as problem of the present invention.

(1) thermotolerance: in having the sheet of identical degree of crystallinity, the sheet that whole mist degree is lower can form finer crystal, in this case, can make resin high-density and crystallization equably, and is highly beneficial to the thermotolerance that improves sheet.

(2) shock resistance: in general, if plastics are applied bigger power then break, power concentrates on the front end in breach (crack), if further apply power, then fissured front end stretches, destroy and enlarge.But, be under the situation below 10% in that whole mist degree is suppressed, be dispersed with micro crystal in the sheet, break and carry out, just run into the micro crystal in the plastics, so disruptive disperses towards periphery.Because 1 breaks greatly to become and severally breaks for a short time, so the party early of breaking is prevented from, the result is favourable to shock resistance like this.

(3) formability: the formability of the sheet of crystallization worsens, but in that whole mist degree is suppressed is 10% below, be dispersed with under the situation of micro crystal, the also dispersion equably in sheet of the needed amorphism part of moulding, thus formability can be kept.

(4) transparency: if make whole mist degree little of below 10%, then the transparency is also good.

Aliphatic polyester sheet of the present invention like this is the degree of crystallinity χ by the layer A that will comprise aliphatic polyester _ABe controlled at 3～60% the suitableeest scope, fully improve the thermotolerance of aliphatic polyester sheet, and by making whole mist degree is below 10%, makes thermotolerance, shock resistance, the transparency, all inventions of establishment simultaneously of formability of aliphatic polyester sheet.

The crystalline size that comprises the above-mentioned layer A of aliphatic polyester is preferably below the 500nm.More preferably below the 300nm, and then be preferably below the 100nm, and then be preferably below the 50nm.From the aspect of improvement thermotolerance, shock resistance, the transparency, formability, the crystalline size that comprises the layer A of aliphatic polyester is to be preferred below the 500nm.In addition, as the lower limit of crystalline size of the layer A that comprises aliphatic polyester, restriction especially is not the smaller the better, but owing to be difficult to make it less than 5nm with present technology, so it is generally acknowledged and be lower limit about 5nm.

From making aspect such as good forming ability, aliphatic polyester sheet of the present invention preferably has above-mentioned layer A and degree of crystallinity χ at least _BSatisfy χ _A＞χ _BComprise aliphatic polyester the layer B.

χ _AWith χ _BRelation χ more preferably _A＞2 χ _BAnd then be preferably χ _A＞3 χ _B, be preferably χ especially _A＞5 χ _Bχ _AWith χ _BRelation satisfy χ _A＞χ _BSituation, be preferred from the aspect of improving effect that increases formability.

The degree of crystallinity χ that comprises the layer B of aliphatic polyester _BPreferable range be 0～30%.Make the degree of crystallinity χ of the layer B that comprises aliphatic polyester _BBe 0～30% scope, mainly the viewpoint from thermotolerance and formability is preferred.Preferred scope is 1～25%, and then preferred range is 2～20%.

In addition, for the layer B that comprises aliphatic polyester, preferred condition is the compound that this layer B contains crystallization nucleating agent and have hydrogen bonded with crystallization nucleating agent.

The described crystalline size that comprises the layer B of aliphatic polyester is preferably below the 500nm.More preferably below the 300nm, and then be preferably below the 100nm, and then be preferably below the 50nm.The crystalline size that comprises the layer B of aliphatic polyester is below the 500nm, is preferred from the aspect that improves thermotolerance, shock resistance, the transparency, formability.In addition, as the lower limit of crystalline size of the layer B that comprises aliphatic polyester, restriction especially is not the smaller the better, but owing in fact be difficult to make it less than 5nm with present technology, so it is generally acknowledged and be lower limit about 5nm.

Have at aliphatic polyester sheet of the present invention under the situation of layer B, in order to bring into play two-layer effect effectively, thickness with respect to whole (aggregate thickness of layer A and layer B), the ratio of layer B (under the situation with the layer B more than 2 layers, being the ratio of layer B total) is preferably 40～98%.Thickness with respect to whole (aggregate thickness of layer A and layer B), the ratio of layer B is (under the situation with the layer B more than 2 layers, ratio for layer B total) satisfied 40～98% situation is preferred from the aspect that thermotolerance and formability are set up simultaneously.Thickness with respect to whole (layer A with layer B aggregate thickness), the ratio of layer B (under situation, being the ratio that layer B adds up to) more preferably 50～95% with the layer B more than 2 layers, and then be preferably 60～90%.

Have at aliphatic polyester sheet of the present invention under the situation of layer B, it both can be 2 layers of formation of layer A and layer B that its lamination constitutes, and also can be 3 layers of formation of layer A/ layer B/ layer A or layer B/ layer A/ layer B, can also be that this above multilayer constitutes.In addition, can also contain other layer the B except that layer A and layer.Other layer except that layer A and layer B, for example, other layer/layer A/ layer B/ layer A, other layer/layer of other layer/layer of layer A/ B/ A etc. are in the aliphatic polyester sheet of the present invention, to the not restriction especially of allocation position on internal layer, top layer etc.Containing under the situation of a layer A, layer other layer the B, the layer A in whole and the ratio of the aggregate thickness of layer B be preferably whole 40～99.9%.Containing under the situation of other layer, the ratio of aggregate thickness of layer A and layer B be whole 40～99.9%, be preferred mainly from keeping whole stable on heating aspect.50～99.5% of more preferably whole of the ratio of the aggregate thickness of layer A and layer B, more preferably 60～99%.

Wherein, aliphatic polyester sheet of the present invention, have dispose in the both sides of layer B layer A, contain layer at least 3 layers the rhythmo structure of A/ layer B/ layer A, in aliphatic polyester sheet of the present invention, be most preferred.This be because by with crystallinity higher relatively the layer A be configured in the top layer, can make sheet when hot briquetting and the oilness of mould good.

Adopt dispose in the both sides of layer A layer B, contain under layer situation of 3 layers the rhythmo structure of B/ layer A/ layer B, be configured in the top layer by the layer B that crystallinity is relatively low, thereby have the advantages such as surperficial mist degree reduction that the gloss that makes the surface is good, surfaceness is caused.On the other hand, from under the situation of aliphatic polyester sheet hot briquetting of the present invention when the hot briquetting and the oilness of mould, stable on heating aspect, preferably contain layer 3 layers the rhythmo structure of A/ layer B/ layer A.

Not restriction especially of whole thickness to aliphatic polyester sheet of the present invention is preferably 50～2000 μ m.100～1500 μ m more preferably, and then be preferably 200～1000 μ m.Sheet breaks, keeps the viewpoint of the intensity of formed body when preventing moulding, and preferred sheet thickness is more than the 50 μ m.In addition, the formability that causes by long-time heating from can prevent moulding time the, the viewpoint of transparency deterioration, preferred sheet thickness is below the 2000 μ m.

The so-called fat adoption ester that uses in the present invention is the polycondensate that is formed by aliphatic dicarboxylic acid and aliphatic dihydroxy alcohol, the polycondensate of aliphatic hydroxyl carboxylic acid etc., but monomeric structure, polymerization process etc. is not limited especially.

Specifically the aliphatic polyester that uses in the present invention can use poly-sebacic acid Aden ester, poly-succinic Aden ester, poly-succinic/hexanodioic acid Aden ester, polypropylene sebacate, the inferior propyl ester of poly-succinic, the inferior propyl ester of poly-succinic/hexanodioic acid, poly(lactic acid), polyoxyethylene glycol acid etc.Wherein, from the environment aspects such as raw material of conduct from plant, aspect of performances such as the transparency, excellent heat resistance set out, and preferably contain poly(lactic acid) as aliphatic polyester.Therefore the fatty family polyester of aliphatic polyester sheet of the present invention preferred layer A and/or layer B is a poly(lactic acid).

In addition, the content of the aliphatic polyester of layer A is preferably 50～100 weight % of the gross weight 100 weight % of layer A.Being under the situation of 50～100 weight % of gross weight of layer A at the content of the aliphatic polyester of layer A, is preferred from the aspect of thermotolerance, shock resistance, good forming ability.Content 60～99.5 weight % more preferably of aliphatic polyester in the gross weight of layer A, and then be preferably 80～99 weight %.Have under the situation of layer B at aliphatic polyester sheet in addition, for layer B too, aliphatic polyester is 50～100 weight % among the gross weight 100 weight % of preferred layer B.The content of aliphatic polyester in the gross weight of layer B is under the situation of 50～100 weight %, is preferred from the aspect of thermotolerance, shock resistance, good forming ability.The content of the aliphatic polyester in the gross weight of layer B is 60～99.5 weight % more preferably, and then are preferably 80～99 weight %.

The so-called poly(lactic acid) of using as the fatty family polyester that constitutes layer A of the present invention, layer B is to be the polymkeric substance of main composition composition with L-lactic acid and/or D-lactic acid units.

So-called poly (l-lactic acid) among the present invention, be meant that proportional surpass 50 moles of % and be the following poly(lactic acid) of 100 moles of % containing of L-lactic acid units in the polylactic acid polymer, from crystalline aspect, preferred L-lactic acid units to contain proportional be 80 moles of %～100 mole %, 95 moles of %～100 mole % more preferably, and then be preferably 98 moles of %～100 mole %.

On the other hand, so-called poly-D-lactic acid among the present invention, be meant that proportional surpass 50 moles of % and be the following poly(lactic acid) of 100 moles of % containing of D-lactic acid units in the polylactic acid polymer, from crystalline aspect, preferred D-lactic acid units to contain proportional be 80 moles of %～100 mole %, 95 moles of %～100 mole % more preferably, and then be preferably 98 moles of %～100 mole %.

Poly (l-lactic acid) is according to the proportional difference that contains of the D-lactic acid units in this poly (l-lactic acid), and the crystallinity of resin itself can change.That is, if the D-lactic acid units in the poly (l-lactic acid) contain increasing proportion, then the crystallinity of poly (l-lactic acid) reduces and near amorphous, if the D-lactic acid units in the opposite poly (l-lactic acid) contain proportional minimizing, then the crystallinity of poly (l-lactic acid) raises.Similarly, poly-D-lactic acid is according to the proportional difference that contains of the L-lactic acid units in this poly-D-lactic acid, and the crystallinity of resin itself can change.That is, if the L-lactic acid units in the poly-D-lactic acid contain increasing proportion, then the crystallinity of poly-D-lactic acid reduces and near amorphous, if the L-lactic acid units in the opposite poly-D-lactic acid contain proportional minimizing, then the crystallinity of poly-D-lactic acid raises.

Poly(lactic acid) as the aliphatic polyester that constitutes layer A of the present invention, layer B uses can contain other monomeric unit except that lactic acid.As other monomer, can enumerate ethylene glycol, propylene glycol, butyleneglycol, heptanediol, hexylene glycol, ethohexadiol, nonanediol, decanediol, 1, the 4-cyclohexanedimethanol, neopentyl glycol, glycerine, tetramethylolmethane, dihydroxyphenyl propane, polyoxyethylene glycol, polypropylene glycol and poly--1, diatomic alcohol compounds such as 4-butyleneglycol, oxalic acid, hexanodioic acid, sebacic acid, nonane diacid, dodecanedioic acid, propanedioic acid, pentanedioic acid, cyclohexane cyclohexanedimethanodibasic, terephthalic acid, m-phthalic acid, phthalic acid, naphthalic acid, two (to carboxyl phenyl) methane, the anthracene dioctyl phthalate, 4,4 '-the diphenyl ether dioctyl phthalate, 5-sodium sulfo isophthalate, dicarboxylic acid such as 5-tetrabutyl Jian Ben Er Jia Suan Phosphonium, oxyacetic acid, hydroxy-propionic acid, hydroxybutyric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxycarboxylic acids such as hydroxy-benzoic acid, caprolactone, valerolactone, propiolactone, the undecane lactone, 1,5-oxepane-2-ketone (1, lactone such as 5-oxepane-2-one).The copolymerization amount of above-mentioned other monomeric unit is under the situation of polylactic acid based resin at the aliphatic polyester that constitutes layer A, layer B, and is all with respect to the monomeric unit of polylactic acid based resin, is preferably 0～30 mole of %, more preferably 0～10 mole of %.

For system film, stretching adaptability and the practical mechanical characteristics that satisfies appropriateness, the weight-average molecular weight of the poly(lactic acid) of using in the aliphatic polyester that constitutes layer A of the present invention, layer B is preferably 50,000～500,000, and more preferably 100,000～250,000.In addition, so-called here weight-average molecular weight is meant and utilizes gel permeation chromatography (GPC) to measure with chloroform solvent, the molecular weight that calculates by the polymethylmethacrylate scaling method.

From whole mist degree can be suppressed littler viewpoint, the poly(lactic acid) of using in the aliphatic polyester that constitutes layer A of the present invention, layer B is preferably by poly (l-lactic acid), form with the mixture of poly-D-lactic acid.If make the crystalline mixtureization of poly (l-lactic acid) and poly-D-lactic acid, then form the different stereocomplex crystal (SC crystal) of crystallographic system with the common crystal (alpha-crystal) that only forms by L-lactic acid or D-lactic acid.There are alpha-crystal and these 2 kinds of crystallographic systems of SC crystal in the same system by making, a kind of crystal growth of the crystallographic system crystal with another crystallographic system can be suppressed, thereby make the further miniaturization of crystal.Promptly, whole mist degree can be suppressed for less by this method.Actual each crystalline method that forms in sheet illustrates in the back, and alpha-crystal and SC crystal are formed simultaneously, also can make one to form earlier, forms after making another person then.As the method that the SC crystal is formed earlier, the preferred decrease temperature crystallineization of using a mouthful mould～curtain coating part.This is to have utilized the SC crystal from comparing the character that the pyritous state begins decrease temperature crystallineization.

Under the situation of using poly(lactic acid) as the aliphatic polyester that constitutes layer A, layer B, poly (l-lactic acid) and poly-D-lactic acid are not limited especially with respect to the cooperation ratio of all poly(lactic acid) in each layer respectively, from above-mentioned purpose, be preferably 1～99%, more preferably 5～95%, and then be preferably 10～90%.Poly (l-lactic acid) and poly-D-lactic acid satisfy the situation of 1～99% scope respectively with respect to the cooperation ratio of all poly(lactic acid) in each layer, be preferred from the aspect of the above-mentioned effect with the crystal miniaturization of easy realization.

In addition, in order to form the SC crystal more expeditiously, the weight-average molecular weight of the poly (l-lactic acid) in preferred each layer (below, be designated as Mw (L)) with the weight-average molecular weight of poly-D-lactic acid (below, be designated as Mw (D)) ratio Mw (L)/Mw (D) or Mw (D)/Mw (L) be 2～40, more preferably 3～20, and then be preferably 4～10.This is because by making the molecular chain length formation difference of poly (l-lactic acid) and poly-D-lactic acid, can make easy near transfiguration mutually, thereby form SC efficiently.Mw in each layer (L) and ratio Mw (L)/Mw (D) or Mw (the D)/Mw (L) of Mw (D) are the situation more than 2, are preferred from forming SC crystalline aspect efficiently.In addition, ratio Mw (L)/Mw (D) or Mw (the D)/Mw (L) of the Mw in each layer (L) and Mw (D) are the situation below 40, are preferred from the aspect of the intensity that can keep the stratified resin of structure.

In the aliphatic polyester sheet of the present invention, from being easy to bring into play the aspect of the crystallization effect that layer A and layer B are expected respectively, preferred D-lactic acid units contains proportional Da (mole %), with the D-lactic acid units with respect to the pass that contains proportional Db (mole %) of all monomeric units in the poly (l-lactic acid) that constitutes above-mentioned layer B is with respect to all monomeric units in the poly (l-lactic acid) that constitutes above-mentioned layer A

Da＜Db。

That is, be the relation of above-mentioned Da＜Db by making Da and Db, the relation of degree of crystallinity of layer A and layer B can be controlled to be χ _A＞χ _B, as a result of be that thermotolerance and formability are set up simultaneously.

As long as layer A in addition at this moment, layer B have poly (l-lactic acid), not restriction especially, layer A, layer B both can only be made of poly (l-lactic acid), it also can be the mixture of poly (l-lactic acid) and poly-D-lactic acid, as long as satisfy Da＜Db (as long as control D-lactic acid units is proportional with respect to containing of all monomeric units in the poly (l-lactic acid) between layer A and layer B), be exactly preferred embodiment.For example can enumerate, be the mixture of poly (l-lactic acid) and poly-D-lactic acid as layer A, is poly (l-lactic acid) as layer B, and satisfy the situation of Da＜Db; Layer A, layer B are the mixtures of poly (l-lactic acid) and poly-D-lactic acid, and satisfy the situation of Da＜Db; Or the like.

With respect to all monomeric units in the poly (l-lactic acid), the D-lactic acid units contain the proportional scope that in layer A, is preferably Da=0.2～4 mole %.Da=0.3～3 mole % more preferably, and then be preferably Da=0.5～2 mole %.With respect to all monomeric units in the poly (l-lactic acid), the D-lactic acid units contain the proportional Db=1～15 mole % that in layer B, is preferably, Db=1.2～10 mole % more preferably, and then be preferably Db=1.5～5 mole %.When in each layer, using the poly (l-lactic acid) more than 2 kinds, use the D-lactic acid units in each poly (l-lactic acid) is contained the mean value that the proportional ratio (quality %) that multiply by corresponding poly (l-lactic acid) is tried to achieve.

In addition, in the aliphatic polyester sheet of the present invention, can in each layer, contain the resin except that aliphatic polyester of 0～80 quality % respectively with respect to the total mass of each layer.As the resin except that aliphatic polyester, for example can enumerate, thermoplastic resins such as polyacetal, polyethylene, polypropylene, polymeric amide, poly-(methyl) acrylate, polyphenylene sulfide, polyether-ether-ketone, polyester, polysulfones, polyphenylene oxide, polyimide, polyetherimide, thermosetting resins such as phenol resins, melamine resin, vibrin, silicone resin, Resins, epoxy, soft thermoplastic resins such as ethylene/methacrylic acid glycidyl ester copolymer, polyester elastomer, polyamide elastomer, ethylene/propene terpolymer, ethene/butene-1 copolymer.Among them, from good with the consistency of aliphatic polyester, particularly poly(lactic acid), as can to improve mixed resin combination second-order transition temperature, the aspect that improves high temperature rigid, preferred poly-(methyl) acrylate.So-called poly-(methyl) acrylate is to serve as to constitute unitary polymkeric substance with at least a kind of monomer being selected from acrylate and the methacrylic ester, also monomer copolymerization more than 2 kinds can be used.The acrylate and the methacrylic ester that use as constituting poly-(methyl) acrylate, for example can use, acrylate such as methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, n-butyl acrylate, cyano ethyl acrylate, cyano group butylacrylic acid ester, and methyl methacrylate, Jia Jibingxisuanyizhi, cyclohexyl methacrylate, methacrylic acid-methacrylic esters such as 2-hydroxy methacrylate.Among them,, preferably use polymethylmethacrylate in order to give higher high temperature rigid of resin combination and formability.

In addition, as the resin except that aliphatic polyester, from giving shock resistance and improving the viewpoint of formability, being preferably selected among layer A and the layer B at least 1 layer, to contain total mass with respect to this layer be that the second-order transition temperature of 0.1～40 quality % is the resin L below 60 ℃.Content is 0.2～30 quality % more preferably, is preferably 0.5～20 quality % especially.From the aspect of the effect that improves the improvement shock resistance, the preferred glass transition temperature is that the content of the resin L below 60 ℃ is more than the 0.1 quality % with respect to the total mass of this layer.In addition, from keeping the transparency and stable on heating aspect, be preferably below the 40 quality %.In addition, from giving the viewpoint of shock resistance and raising formability, preferably contain resin L among the layer B at least.

Mainly from keep stable on heating viewpoint and with the viewpoint of the intermiscibility of aliphatic polyester based resin, the weight-average molecular weight of this resin L is preferably 2,000～200,000, more preferably 5,000～100,000, be preferably 10,000～80,000 especially.In addition, so-called here weight-average molecular weight is meant and utilizes gel permeation chromatography (GPC) to measure with chloroform solvent, the molecular weight that calculates by the polymethylmethacrylate scaling method.

As resin L, preferably use segmented copolymer, polyester, rubber of polyester or polyalkylene ether and poly(lactic acid) etc.

Using under the situation of polyester as resin L, preferably the total mass with respect to the layer that contains this resin L (polyester) contains 0.1～10 quality %.Content is 0.2～5 quality % more preferably, is preferably 0.5～3 quality % especially.

As the polyester that resin L preferably uses, can preferably use aromatic series and/or aliphatic polyesters such as poly terephthalic acid Aden ester, polytrimethylene terephtalate, poly-sebacic acid Aden ester, poly-succinic Aden ester, poly-succinic/terephthalic acid Aden ester, poly-hexanodioic acid/terephthalic acid Aden ester, poly-succinic/hexanodioic acid Aden ester, polypropylene sebacate, the inferior propyl ester of poly-succinic, the inferior propyl ester of poly-succinic/terephthalic acid, the inferior propyl ester of poly-hexanodioic acid/terephthalic acid, the inferior propyl ester of poly-succinic/hexanodioic acid.Among them, to giving the especially effectively poly-hexanodioic acid of shock resistance/terephthalic acid Aden ester and poly-succinic/hexanodioic acid Aden ester.

Under the segmented copolymer that uses polyester or polyalkylene ether and poly(lactic acid), the situation of rubber as resin L, preferably the total mass with respect to the layer that contains this resin L (segmented copolymer of polyester or polyalkylene ether and poly(lactic acid), rubber) contains 5～40 quality %.Content more preferably 7～30 quality %, be preferably 10～20 quality % especially.

Be the segmented copolymer that forms by polyester segment or polyalkylene ether segment and polylactic acid chain segment as the segmented copolymer of the polyester of resin L or polyalkylene ether and poly(lactic acid) in addition.The content of lactic component is preferably greater than 0 quality % in this segmented copolymer of 100 quality % and is below the 60 quality % in this segmented copolymer.In this segmented copolymer, lactic component satisfies greater than 0 quality % in this segmented copolymer of 100 quality % and is the situation of the scope below the 60 quality %, and the aspect that raises from the effect that improves rerum natura is preferred.And then be under the situation of poly(lactic acid) at the aliphatic polyester of the layer of this segmented copolymer of use of aliphatic polyester sheet of the present invention, have more than one molecular weight in preferred especially this segmented copolymer a part and be the polylactic acid chain segment more than 1,500.In this case, the polylactic acid chain segment of this segmented copolymer, by mixing by in the formed crystal of poly(lactic acid) as the aliphatic polyester of mother metal, thereby produce and make the polylactic acid chain segment of segmented copolymer and the effect that mother metal is connected and fixed, can suppress this segmented copolymer and ooze out (bleed out).

As the polyester segment of in segmented copolymer, using, preferably use poly terephthalic acid Aden ester, polytrimethylene terephtalate, poly-sebacic acid Aden ester, poly-succinic Aden ester, poly-succinic/terephthalic acid Aden ester, poly-hexanodioic acid/terephthalic acid Aden ester, poly-hexanodioic acid/Succinic Acid Aden ester, polypropylene sebacate, the inferior propyl ester of poly-succinic, the inferior propyl ester of poly-succinic/terephthalic acid, the inferior propyl ester of poly-hexanodioic acid/terephthalic acid, poly-hexanodioic acid/inferior propyl ester of Succinic Acid etc. as resin L.

As above-mentioned polyalkylene ether segment, can preferably use polyoxyethylene glycol, polypropylene glycol, gather-1,4-butyleneglycol, polyethylene glycol-propylene glycol copolymers etc.

As the above-mentioned rubber of resin L, preferably contain the polymkeric substance that silicone component, acrylic component, vinylbenzene composition, nitrile composition, conjugated diolefine composition, urethane composition or ethylene, propylene become to grade in addition, be more preferably hud typed multilayer structure polymer.

To aliphatic polyester sheet of the present invention, it is important that described layer A contains crystallization nucleating agent.Further have at aliphatic polyester sheet under the situation of layer B, preferred condition is that not only layer A has crystallization nucleating agent but also layer B also has crystallization nucleating agent.The effect of this crystallization nucleating agent is suppress to form that the crystal of the aliphatic polyester of each layer is excessively grown up and with the crystal miniaturization, and improves crystallization speed.As crystallization nucleating agent, can use aliphatics carboxylic acid amides, N-to replace urea, aliphatic carboxylate, fatty alcohol, aliphatic carboxylic acid esters,, aliphatic/aromatic carboxylic hydrazides, Sorbitol Powder based compound, melamine based compound, phenyl-phosphonic acid metal-salt, amino acid, polypeptide etc. with such effect.Wherein, the preferred compound that is selected from aliphatics carboxylic acid amides, Sorbitol Powder based compound, amino acid, the polypeptide that uses.

Concrete example as the aliphatics carboxylic acid amides that is preferably used as crystallization nucleating agent, can enumerate laurylamide, palmitic amide, oleylamide, stearylamide, mustard acid amides Shan Yu acid amides, the Viscotrol C acid amides, aliphatic monocarboxylic acid amidess such as hydroxyl stearylamide, N-oil base palmitic amide, N-oil base oleylamide, N-oil base stearylamide, N-octadecyl oleylamide, N-octadecyl stearylamide, N-octadecyl mustard acid amides, the methylol stearylamide, N-such as methylol Shan Yu acid amides replace the aliphatic monocarboxylic acid amides, methylene radical distearyl acid amides, the ethylene laurylamide, the ethylene decyl amide, the ethylene oleylamide, ethylene bis stearamide, ethylene mustard acid amides, ethylene Shan Yu acid amides, ethylene isostearoyl amine, ethylene hydroxyl stearylamide, butylidene distearyl acid amides, hexa-methylene two oleylamide, hexa-methylene distearyl acid amides, hexa-methylene Er Shan Yu acid amides, hexa-methylene dihydroxyl stearylamide, between xylylene distearyl acid amides, between aliphatic carboxylic acid diamide such as xylylene two-12-hydroxyl stearylamide, N, N '-two oil base sebacoyl amine, N, N '-two oil base adipamide, N, N '-two (octadecyl) adipamide, N, N-such as N '-two (octadecyl) sebacoyl amine replace the aliphatic carboxylic acid diamide.Wherein, the preferred compound that is selected from aliphatic monocarboxylic acid amides, N-replacement aliphatic monocarboxylic acid amides and aliphatic carboxylic acid diamide that uses.Preferred to use preferred carbonatoms be 4～30, more preferably carbonatoms is 12～30 aliphatic carboxylic acid, the acid amides that forms with amine in the monoamine/diamines of the aliphatic/aromatic that is selected from ammonia or carbonatoms 1～30.The preferred especially compound that is selected from palmitic amide, stearylamide, mustard acid amides, mountain Yu acid amides, Viscotrol C acid amides, hydroxyl stearylamide, N-oil base palmitic amide, N-octadecyl mustard acid amides, ethylene decyl amide, ethylene oleylamide, ethylene bis stearamide, ethylene laurylamide, ethylene mustard acid amides, an xylylene distearyl acid amides and xylylene two-12-hydroxyl stearylamide that uses.

In addition, concrete example as preferably replace urea as the N-of crystallization nucleating agent use can use N-butyl-N '-octadecyl urea, N-propyl group-N '-octadecyl urea, N-octadecyl-N '-octadecyl urea, N-phenyl-N '-octadecyl urea, xylylene two (octadecyl) urea, tolylene two (octadecyl) urea, hexa-methylene two (octadecyl) urea, ditan two (octadecyl) urea, ditan two (dodecyl) urea etc.

In addition, the metal-salt that as the aliphatic carboxylate's who preferably uses as crystallization nucleating agent preference, can preferably enumerate carbonatoms and be 4～30, more preferably carbonatoms is 14～30 aliphatic carboxylic acid.Be the concrete example of 14～30 aliphatic carboxylic acid as carbonatoms, can enumerate lauric acid, tetradecanoic acid, palmitinic acid, oleic acid, stearic acid, Unimac 5680, docosoic, montanic acid etc.In addition, as the example of metal, can enumerate lithium, sodium, potassium, magnesium, calcium, barium, aluminium, zinc, silver, copper, lead, thallium, cobalt, nickel, beryllium etc.The preferred especially salt that uses stearic salt, montanic acid, the preferred especially compound that is selected from sodium stearate, potassium stearate, Zinic stearas and montanic acid calcium that uses.

In addition, as the preference of the fatty alcohol that preferably uses as crystallization nucleating agent, can enumerate carbonatoms is 4～30, more preferably carbonatoms is 15～30 fatty alcohol.Specifically, can enumerate aliphatic monobasic alcohol classes such as pentadecylic alcohol, cetyl alcohol, heptadecanol, Stearyl alcohol, nonadecanol, eicosanol, n-Hexacosanol, triacontanol price quote, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1, aliphatic polyol classes such as 9-nonanediol, decamethylene-glycol, pentamethylene-1,2-glycol, hexanaphthene-1,2-glycol, hexanaphthene-1, ring-type alcohols such as 4-glycol etc.Especially preferably use the aliphatic monobasic alcohol class, especially preferably use Stearyl alcohol.

In addition, preference as the aliphatic carboxylic acid esters, who preferably uses as crystallization nucleating agent, preferred to use preferred carbonatoms be 4～30, more preferably carbonatoms is 12～30 aliphatic carboxylic acid, the ester that forms with alcohol in monohydroxy-alcohol, dibasic alcohol and the trivalent alcohol of the aliphatic/aromatic that is selected from carbonatoms 1～30.As concrete example, can enumerate the lauric acid cetyl ester, the lauric acid phenacyl ester, the tetradecanoic acid cetyl ester, the tetradecanoic acid phenacyl ester, the palmitinic acid isopropyl esters, the palmitinic acid dodecyl ester, palmitinic acid tetradecyl ester, palmitinic acid pentadecane ester, the palmitinic acid stearyl, the palmitinic acid cetyl ester, the palmitinic acid phenylester, the palmitinic acid phenacyl ester, aliphatic monocarboxylic acid ester classes such as stearic acid cetyl ester docosoic ethyl ester, the mono laurate glycol ester, single palmitinic acid glycol ester, the monoesters class of ethylene glycol such as Tego-stearate, two lauric acid glycol esters, two palmitinic acid glycol esters, the diester class of ethylene glycol such as diglycol stearate, glyceryl monolaurate, single tetradecanoic acid glyceryl ester, monopalmitin, the monoesters class of glycerine such as glyceryl monostearate, GLYCERYL DILAURATE, two (tetradecanoic acid) glyceryl ester, glycerol-1,3-dipalmitate, the diester class of glycerine such as distearin, trilaurin, three (tetradecanoic acid) glyceryl ester, tripalmitin, Tristearoylglycerol, two oleic acid, one palmitin, distearyl acid one palmitin, three ester classes of glycerine such as distearyl acid monooleate glyceryl ester etc.Wherein the diester class of preferred ethylene glycol is especially preferably used diglycol stearate.

In addition, concrete example as the aliphatic/aromatic carboxylic hydrazides that preferably uses as crystallization nucleating agent, can use the sebacic acid dibenzoyl hydrazine, concrete example as the Sorbitol Powder based compound, can use dibenzylidene sorbitol, two (to the methyl benzylidene) Sorbitol Powder, two (to the ethyl benzylidene) Sorbitol Powder, two (3, the 4-dimethyl benzylidene) Sorbitol Powder, concrete example as the melamine based compound, can use melamine cyanurate and poly-vinic acid (acid of Port リ PVC Application) melamine, as the concrete example of Phenylsulfonic acid metal-salt, can use the phenyl-phosphonic acid zinc salt, the phenyl-phosphonic acid calcium salt, phenyl-phosphonic acid magnesium salts etc.

In addition, as the amino acid whose concrete example that preferably uses as crystallization nucleating agent, can use as the glycine, L-Ala, Xie Ansuan, leucine, Isoleucine, Serine, Threonine, halfcystine, methionine(Met), phenylglycocoll, tryptophane, proline(Pro), adjacent tyrosine, L-glutamic acid, aspartic acid, glutamine, l-asparagine, Methionin, arginine, the Histidine that constitute the contained proteinic key element of organism, can use Leuprolide (leuprolide) etc. as the concrete example of polypeptide.

These crystallization nucleating agents both may be used alone, two or more kinds can also be used in each layer.If more than 2 kinds and usefulness, then to compare with situation about using separately respectively, performance synergy separately increases crystallization speed sometimes, promotes that the crystal miniaturization is more remarkable.

For the total content of these crystallization nucleating agents, about layer A,, preferably contain 0.1～5 quality % with respect to the total mass of layer A, 0.3～3 quality % more preferably, and then be preferably 0.5～2 quality %.From can bringing into play the aspect of the thermotolerance and the transparency, the total content of the crystallization nucleating agent of preferred layer A be more than the 0.1 quality % of total mass of layer A.In addition, saturated from effect as crystallization nucleating agent, and can prevent to cause the aspect of outward appearance, rerum natura variation to set out, preferred content is below the 5 quality %.

In addition,,, preferably contain the crystallization nucleating agent of 0.05～3 quality % with respect to the total mass of layer B about layer B, 0.08～2 quality % more preferably, and then be preferably 0.1～1.5 quality %.From can bringing into play the viewpoint of the thermotolerance and the transparency, the total content of the crystallization nucleating agent of preferred layer B be more than the 0.05 quality % of total mass of layer B.In addition, from keeping the aspect of formability, preferred content is below the 3 quality %.

In the aliphatic polyester sheet of the present invention, it is important further containing the compound that has a hydrogen bonded with above-mentioned crystallization nucleating agent.Further have under the situation of layer B at aliphatic polyester sheet in addition, preferred mode is the layer A compound that contains crystallization nucleating agent and have hydrogen bonded with crystallization nucleating agent not only, and the layer B compound that also contains crystallization nucleating agent and have hydrogen bonded with crystallization nucleating agent.Above-mentioned illustrative crystallization nucleating agent mostly is self combination, and in this case, crystallization nucleating agent is added in the resin under the agglutinative state, makes troubles for sometimes the crystalline miniaturization.Therefore, by the compound that further mixing and crystallization nucleating agent have hydrogen bonded, can make this crystallization nucleating agent sometimes self in conjunction with decomposition, make crystallization nucleating agent further little decentralized.In this case, the crystallization miniaturization becomes more effective.

To with crystallization nucleating agent have hydrogen bonded this compound addition means especially the restriction.The compound that has hydrogen bonded with crystallization nucleating agent both can mix with aliphatic polyester, crystallization nucleating agent fusion simultaneously or solution, also can add in the aliphatic polyester in advance with after crystallization nucleating agent fusion or solution mix.In addition, also can utilize the method for master batch (master pellet) made from its dilution.Among them, self the bonded viewpoint from the decomposition and crystallization nucleator preferably will have the compound of hydrogen bonded with crystallization nucleating agent, mix with crystallization nucleating agent fusion or solution in advance, add the method in the aliphatic polyester then to.

In addition, judge whether this compound and crystallization nucleating agent have hydrogen bonded, can utilize NMR to analyze.For example, can be with the solution mixture of this compound and crystallization nucleating agent ¹The H-NMR wave spectrum is compared with each monomeric situation, changes from chemical shift and confirms to have or not hydrogen bond.For example, use amide compound as crystallization nucleating agent, use the Sorbitol Powder based compound as and crystallization nucleating agent between have under the situation of compound of hydrogen bonded, in solution mixture, compare with monomer separately, the proton peak of amido linkage is to the downfield displacement, the proton peak of the hydroxyl of Sorbitol Powder can confirm to exist between the two hydrogen bond thus to upfield shift.

As having the concrete example of the compound of hydrogen bonded,, can use aliphatics alcohols, Sorbitol Powder based compound, amino acid, polypeptide etc. using aliphatics carboxylic acid amides, N-to replace under the situations as crystallization nucleating agent such as urea with crystallization nucleating agent.Therefore, preferred especially the use is selected from aliphatics carboxylic acid amides and N-and replaces in the urea at least a kind as crystallization nucleating agent, the compound that uses at least a kind of conduct being selected from aliphatics alcohols, Sorbitol Powder based compound, amino acid and the polypeptide and crystallization nucleating agent to have hydrogen bonded.

Have under the situation of compound of hydrogen bonded containing with crystallization nucleating agent, magnitude relation with crystallization nucleating agent is not limited especially, but from self bonded viewpoint of decomposition and crystallization nucleator effectively, crystallization nucleating agent and be preferably 1: 9～9: 1 with weight ratio that crystallization nucleating agent has a compound of hydrogen bonded.More preferably 1: 5～5: 1, and then be preferably 1: 2～2: 1.

From above-mentioned decomposition and crystallization nucleator self in conjunction with, with crystallization nucleating agent little decentralized viewpoint resin, can also use only crystallization nucleating agent once to be dissolved in the solvent and to decompose self combination, be added on method such in the resin then.

Can contain various particles in each layers such as the layer A of aliphatic polyester sheet of the present invention, layer B.By containing particle, can make the oilness of forming mould and sheet good, and the reduction moulding is inhomogeneous, the sheet fracture, in addition, also can make from the release property of mould good.The median size of various particles is preferably 0.01～10 μ m, and the content in each layer preferably contains 0.01～10 quality % with respect to the total mass of the constituent of each layer.The median size of various particles is 0.02～5 μ m more preferably, and then is preferably 0.03～2 μ m.Content in each layer is 0.02～1 quality % with respect to the total mass of the constituent of each layer more preferably, and then is preferably 0.03～0.5 quality %.From the bigger aspect of effect of the oilness of improvement forming mould and sheet, preferably median size is more than the 0.01 μ m, or the content in each layer is more than the 0.01 quality % of total mass of constituent of each layer.On the other hand, from the aspect of the transparency that can keep film, preferred median size is below the 10 μ m, or the content in each layer is below the 10 quality % of total mass of each layer.

The kind of particle can suitably be selected according to purpose, purposes, and only otherwise damaging effect of the present invention get final product, restriction especially can be enumerated inorganic particulate, organic filler, cross-linked polymer particle, the interior inner particles that is generated of polymerization system etc.Certainly, each particle both can be used alone, but also also mix together respectively.Under situation about mix using, make that the median size of particle of each kind is get final product in the scope of 0.01～10 μ m, in addition, make that the total content of particle in each layer of all kinds is to get final product in the scope of 0.01～10 quality % of this layer.

In addition, in each layer of layer A, the layer B etc. of aliphatic polyester sheet of the present invention, so long as do not damage the scope of effect of the present invention, promptly can cooperate additive as required in right amount, for example, tinting materials such as defoamer, pigment, dyestuff such as the organic lubricant of fire retardant, thermo-stabilizer, photostabilizer, antioxidant, anti-coloring agent, UV light absorber, antistatic agent, softening agent, tackifier, fatty acid ester, wax etc. or polysiloxane.

In addition, in order to prevent adhesion, prevent static, give release property, improve traumatic resistance, to reduce surperficial mist degree etc., can also functional layer be set on the surface of aliphatic polyester sheet of the present invention by surface smoothingization.In order to form this functional layer, can use the online coating method that in the manufacturing process of sheet, carries out, the off-line coating method that after sheet is batched, carries out etc.

As the concrete method that is used to form the above-mentioned functions layer, can be with the excellent coating method of coiling, scrape that the skill in using a kitchen knife in cookery, nick version coating method, gravure roll coating method, reverse roll coating method, airblade coating method, bar are coated with method, mould is coated with method, licks the method for being coated with, reverses and lick the method for being coated with, pickling process, curtain coating method, spraying method, air doctor blade coating method or the coating process except that these application or applied in any combination separately.

In addition, example as online coating method, the method that coating masking liquid on no drawing sheet is arranged, on no drawing sheet, be coated with masking liquid, then successively or simultaneously biaxial stretch-formed method, on the sheet behind the uniaxial extension, be coated with masking liquid, further along with before the rectangular direction tensile of uniaxial extension direction method, or on biaxial stretch-formed this masking liquid of coating, further tensile method etc. then.

In addition, in order to improve coating and the cohesiveness of masking liquid on sheet, can before coating, carry out chemical treatment, discharge process to aliphatic polyester sheet of the present invention.

Preferably at least one mask at aliphatic polyester sheet of the present invention has release layer.This is the reason because of following explanation, and crystallization is brought into play thermotolerance thereby aliphatic polyester sheet promptly of the present invention is sometimes by the interior thermal treatment of forming mould, and at this moment, the release property between sheet and the mould is good.

Material as this release layer, can use material known, preferred use be selected from long-chain aliphatic acrylate, silicone resin, melamine resin, fluoro-resin, derivatived cellulose, urea resin, polyolefin resin, the alkane hydrocarbon system releasing agent etc. more than a kind.

In addition, preferably antistatic backing is arranged at least one mask of aliphatic polyester sheet.

Material as this antistatic backing can use material known, and preferred main chain has the antistatic agent of quaternary ammonium salt.In addition, contain at least a kind multipolymer of sulfonic acid, sulfonate, vinyl imidazole salt, dianiline ammonium chloride, alkyl dimethyl ammonium chloride, alkyl ether sulphate, can give static electricity resistance by making this material.

Aliphatic polyester sheet of the present invention reduces from suppressing to decompose the intensity that causes, and is set out in the good aspect of thermotolerance, and the C-terminal concentration that preferably constitutes the aliphatic polyester based resin of sheet is 0.1～30 equivalent/10 ³Kg, more preferably 0.5～20 equivalent/10 ³Kg is preferably 1～10 equivalent/10 especially ³Kg.From when aliphatic polyester sheet or its formed body under the how wet conditions of high temperature or with condition that hot water contact under when using, can prevent that the aspect of the intensity reduction that hydrolysis causes from setting out, the C-terminal concentration of preferred aliphat polyester based resin is 30 equivalents/10 ³Below the kg.That is, under the situation about in purposes such as container, using, can prevent that this container becomes fragile and such problem such as easily break.

As making C-terminal concentration is 30 equivalents/10 ³The method that kg is following, for example can enumerate, catalyzer when synthesizing, the method that thermal history is controlled by aliphatic polyester based resin, the method for the thermal history of reduction aliphatic polyester sheet when extruding the system film, the method that use response type compound seals C-terminal etc.As the response type compound, for example can enumerate, condensation reaction such as fatty alcohol, amide compound type compound, addition reaction-type compounds such as carbodiimide compound, epoxy compounds, oxazoline compound, the aspect that is difficult for generating unnecessary by product during from reaction, preferred addition reaction-type compound.

Aliphatic polyester sheet of the present invention is under the situation of poly(lactic acid) at aliphatic polyester, and to become component be 0 quality %～0.3 quality % to contained lactic acid oligomer in the preferred sheet.0 quality %～0.25 quality % more preferably, and then be preferably 0 quality %～0.2 quality %.From can make this sheet residual lactic acid oligomer composition with the Powdered or aqueous aspect of separating out, prevent operability and transparency deterioration, and can make the polylactic resin hydrolysis, prevent that the aspect that the weather resistance of sheet worsens from setting out, preferably in this sheet contained lactic acid oligomer to become component be below the 0.3 quality %.Here so-called lactic acid oligomer composition, being meant the amount cyclic dimer maximum, representational lactic acid (rac-Lactide) in the wire oligopolymer, cyclic oligomer etc. of existing lactic acid, lactic acid in sheet, is LL-rac-Lactide and DD-rac-Lactide, DL (meso)-rac-Lactide.

The stress F when stretching for 70 ℃ following 100% of a direction in the face of the preferred sheet at least of aliphatic polyester sheet of the present invention ₁₀₀Be 1～10MPa.1.5～9Mpa more preferably, and then be preferably 2～8MPa.From the aspect of the good forming ability that makes sheet, preferred 70 ℃ of 100% stress F when stretching down ₁₀₀Below 10MPa.On the other hand, if 70 ℃ of following 100% stress F when stretching ₁₀₀More than 1MPa, be preferred then from the good aspect of the thermotolerance of sheet.

Aliphatic polyester sheet of the present invention both can be a drawing sheet not, also can be drawing sheet, and restriction especially from the viewpoint of weather resistance, can be a drawing sheet mainly, at this moment preferably biaxial stretch-formed.

Obtain the method for drawing sheet, can by inflation method, simultaneously biaxial stretch-formed method, known stretching piece making method such as biaxial stretch-formed method carries out successively.The calm directed state that has formability and stable on heating aliphatic polyester sheet of the present invention concurrently easy to control, and can be set out in the aspect of film speed high speed preferably biaxial stretch-formed successively method.

Then, be that the situation of poly(lactic acid) is an example with aliphatic polyester, specifically describe the manufacture method of aliphatic polyester sheet of the present invention.

Poly(lactic acid) among the present invention can obtain with following method.As raw material, use the lactic component of L-lactic acid and/or D-lactic acid, but can also and use the hydroxycarboxylic acid except that lactic component.Can also use cyclic ester intermediate, for example rac-Lactide, glycollide etc. as raw material in addition.And then can also and use omega-dicarboxylic acids, di-alcohols etc.

Poly(lactic acid) can be by obtaining with the method for the direct dehydrating condensation of above-mentioned raw materials or with the method for above-mentioned cyclic ester intermediate ring-opening polymerization.For example, under the situation that directly dehydrating condensation is made, obtain high molecular weight polymers by utilizing following method to carry out polymerization, described method be with the lactic acid class or, lactic acid class and hydroxycarboxylic acid be preferably at organic solvent, preferably carry out the azeotropic dehydration condensation in the presence of the phenyl ether series solvent, remove in the solvent that will distill out from azeotropic then to anhydrate and make the method that the solvent that is essentially anhydrous state is sent reaction system back to.In addition, people also know by with catalyzer such as cyclic ester intermediates such as rac-Lactide use stannous octoates, under reduced pressure carry out ring-opening polymerization, also can obtain high molecular weight polymers.At this moment, can obtain the less polymkeric substance of rac-Lactide amount by using following method, make catalyst deactivation after the method for the moisture when described method is the reflux of adjusting in the organic solvent and the condition of removing of low molecular compound, polyreaction finish and suppress the method for depolymerization reaction, method that the polymkeric substance of making is heat-treated etc.

To being used for aliphatic polyester sheet of the present invention is made the restriction especially of method of the degree of crystallinity of requirement, can use in the sheet film-forming process in the decrease temperature crystallineization of mouth mould～curtain coating part, the intensification crystallization that in the warming mill carrying or by tenter machine, is undertaken, by single shaft or the biaxial stretch-formed oriented crystallization that carries out, (off-line) undertaken by reheat after sheet system film intensification crystallization etc.These methods both may be used alone, two or more kinds can also be used.

Here, the poly(lactic acid) sheet merge being used, and be example by the biaxial stretch-formed successively situation of carrying out oriented crystallization of tenter machine formula in the decrease temperature crystallineization of mouth mould～curtain coating part and the situation of the intensification crystallization in the warming mill carrying, be specifically described.

With poly-L-lactic acid resin and poly-D lactic acid resin respectively under the reduced pressure below 5 holders, 100～120 ℃ of dryings more than 3 hours, the resin of A layer usefulness and the resin of B layer usefulness are added independently each forcing machine respectively, according to melt viscosity, carry out melting mixing at 150～250 ℃.Here, in mouth mould～curtain coating part decrease temperature crystallineization, the mouth mould is cooled to 120～200 ℃ in advance according to the decrease temperature crystalline temperature of resin.Outside die head or in the die head, carry out compoundization, by of the slit-shaped mouth mould ejection of T modulus method from antelabium interval 1～3mm.The resin of ejection in metal cooling but on the curtain coating rotary drum, is used the wire electrode of diameter 0.5mm to apply static and makes its adhesion, thereby obtain omnidirectional cast sheet.

In order to promote above-mentioned decrease temperature crystallineization, the metal cooling but surface temperature of roller can be preferably 0～50 ℃ scope usually near the temperature the decrease temperature crystalline temperature of resin, and more preferably scope is 5～40 ℃, and then preferable range is 10～30 ℃.By with metal cooling but the surface temperature of roller be set at this scope, can prevent that metallic roll and sheet are bonding, in addition, can bring into play the good transparency.

Crystallization changes into the degree of crystallinity of requirement by carrying on warming mill with the omnidirectional cast sheet that obtains like this.The preferred range of the warming mill of the highest temperature is 60～160 ℃, more preferably 70～150 ℃ and then be preferably 80～140 ℃.Bonding in order to prevent sheet, the warming mill surface is preferably siloxanes, テ Off ロ Application (registered trademark) material.The final surface temperature of sheet at this moment is preferably 70～150 ℃, and more preferably 80～140 ℃, and then be preferably 90～130 ℃.Next, reduce the sheet temperature by carrying on 0～50 ℃ cooling roller, thereby obtain not having the tensile sheet.

Carrying out under the biaxial stretch-formed successively situation of tenter machine formula,, indulging the tensile temperature on warming mill thereby be warming up to by the above-mentioned omnidirectional cast sheet that obtains is carried.During intensification can and with assisted heating devices such as infrared heaters.The preferable range of draft temperature is 70～95 ℃, more preferably 75～90 ℃.Utilize the roll surface speed multistage poor, that carry out more than 1 section or 2 sections along the leaf length direction between the warming mill to stretch with omnidirectional after heating up like this.The stretching ratio that adds up to is preferably 1.2～3.5 times, more preferably 1.5～3.0 times.

Sheet behind such uniaxial extension is temporarily cooled off, then with the both ends of sheet with the clip clamping and import tenter machine, carry out the stretching of width.Draft temperature is preferably 70～95 ℃, more preferably 75～90 ℃.Stretching ratio is preferably 1.2～3.5 times, more preferably 1.5～3.0 times.For the poor performance of the width that reduces sheet, preferably under temperature, carry out the stretching of width than low 1～15 ℃ of the draft temperature of length direction.And then as required, can carry out once more longitudinal stretching and/or cross directional stretch once more.

Then, with this drawing sheet under tension or broad ways carry out heat setting in lax.Mainly from the viewpoint of giving the sheet thermal dimensional stability with rac-Lactide contained the sheet is dispersed and reduce the viewpoint of rac-Lactide amount, preferred thermal treatment temp is 100～160 ℃, more preferably 120～150 ℃.Heat treatment time is preferably 0.2～30 second scope.Relaxation rate is preferably 1～8% from the viewpoint of the percent thermal shrinkage that reduces width, and more preferably 2～5%.And then preferably temporarily sheet is cooled off before handling carrying out heat setting.

And then, if necessary,, sheet is cooled to room temperature and batches, thereby obtain aliphatic polyester sheet as target then when length and width carry out relaxation processes.

Then, describe for the formed body that constitutes by aliphatic polyester sheet of the present invention below.

So-called formed body among the present invention comprises film, bag, pipe, sheet, cup, bottle, dish, line etc., does not limit about its shape, size, thickness, outward appearance etc.Wherein, can preferably enumerate, the conformal utensil classes of in the demonstration package of commodity is used, using such as blister plastic packaging, container classes such as the displaying of food disc, Drink dispenser bottle, packed meal case, beverage cup, various Industrial materials such as other various wrapping formed bodys and surfacing.

As forming method, can use vacuum forming, vacuum is pressed the various methods of forming such as empty moulding, the moulding of plunger pressing aid, straight line moulding, free drawing (free drawing) moulding, plug ring moulding, skeleton forming.

From the stable on heating viewpoint of further raising formed body, preferably when moulding or after the moulding, heat-treat.As this method, the method that can use the method for directly carrying out crystallization in the mould when moulding (below, be called mould intercrystalline method), non-crystalline formed body of this sheet is heat-treated.

In mould intercrystalline method, the design temperature condition optimization of mould is the temperature range of second-order transition temperature (the Tg)～fusing point (Tm) of aliphatic polyester sheet, more preferably (Tg+5) ℃～(Tm-20) ℃, and then be preferably (Tg+10) ℃～(Tm-40) ℃.Here be that the situation about forming of the diverse multilayer by resin is inferior at aliphatic polyester sheet, when observing a plurality of second-order transition temperature as aliphatic polyester sheet, use value minimum in the second-order transition temperature of each layer as Tg, use value minimum in the fusing point of each layer as Tm.Be higher than at design temperature under the situation of Tm,, damage the transparency, the warpage of formed body sometimes though can make it crystallization at short notice, and if then long-time heating then sometimes the fusing.Be lower than under the temperature of Tg on the contrary, crystallization speed significantly reduces.The heat treated hold-time is also according to the difference of the formation of aliphatic polyester sheet and difference so long as be enough to make above get final product of time of formed body sufficient crystallisingization, does not limit especially.

Embodiment

Show that below embodiment is described more specifically the present invention, but the present invention is not subjected to any restriction of these embodiment.

[measuring and evaluation method]

Mensuration shown in the embodiment, evaluation are carried out under the following conditions.

(1) degree of crystallinity χ _A, χ _B

Sheet is cut into appropriate size, be fixed on the aluminum specimen holder and (on 20mm * 18mm * 0.15mmt), under following condition determination, carry out wide-angle x-ray and measure.

Use the system RU-200R (rotating cathode type) of motor of science (strain) society (x-ray source: CuK α line (using the flexure crystal monochromator) as X-ray generator, output rating: 50kV, 200mA), use motor of science (strain) society system 2155D type (slit: 1 °-0.15mm-1 °-0.45mm as goniometer, detector: scintillometer), use the system RAD-B of motor of science (strain) society type as the count recording device, at condition determination [2 θ/θ: continuous sweep, measurement range: 2 θ=5～145 °, step (step): 0.02 °, sweep velocity: 2 °/minute] under carry out wide-angle x-ray and measure, obtain degree of crystallinity by the Ruland method.

(2) crystalline size

(2a)

With sheet along (I) parallel with length direction and with the vertical direction of the face of sheet, (II) parallel with width and with the vertical direction of the face of sheet, (III) direction parallel with the face of sheet, make sample with the ultrathin sectioning cutting respectively, dye as required, use transmission electron microscope (the system H-7100FA of Hitachi type), under the condition of pressurization voltage 100kV, observe cut surface, take pictures (here with 40,000 times, can't see under the crystalline situation of diameter above the size of 100nm, or under the crystal situation about not existing, obtain crystalline size) with the method that following (2b) illustrates as island component.

With resulting photo in image dissector as image capture, select any 10 (under the situation of 10 of less thaies for all existence) island components, by carrying out picture processing, the following size of obtaining island component like that.

Obtain the maximum length (le) of leaf length direction of the island component that occurs on the cut surface of maximum length (ld), (III) of the maximum length (lc) of sheet thickness direction of the island component that occurs in the cutting of maximum length (lb), (II) of the maximum length (la) of sheet thickness direction of the island component that occurs on the cut surface of (I) and length direction and width and the maximum length (lf) of width.Next, under the situation of the shape index I=of island component (mean value of mean value+le of lb)/2, shape index J=(mean value of mean value+lf of ld)/2, shape index K=(mean value of mean value+lc of la)/2, crystalline size is (I+J+K)/3.

(2b)

Sheet is cut into appropriate size, be fixed on the aluminum specimen holder and (on 20mm * 18mm * 0.15mmt), under following condition determination, carry out wide-angle x-ray and measure.

Use the system RU-200R (rotating cathode type) of motor of science (strain) society (x-ray source: CuK α line (using the flexure crystal monochromator) as X-ray generator, output rating: 50kV, 200mA), use motor of science (strain) society system 2155D type (slit: 1 °-0.15mm-1 °-0.45mm as goniometer, detector: scintillometer), use the system RAD-B of motor of science (strain) society type as the count recording device, at condition determination [2 θ/θ: continuous sweep, measurement range: 2 θ=5～145 °, step: 0.02 °, sweep velocity: 2 °/minute] under carry out wide-angle x-ray and measure, use Scherrer (Scherrer) formula to obtain crystalline size from the peak width at half height of diffraction peak.

(3) mist degree

Use haze meter (Japanese electric look industry (strain) system NDH5000) to measure the haze value of sheet.Carry out 5 times based on 1 level and measure,, obtain haze value (%) with the form of the scaled value of the situation of the sheet of thickness 0.4mm from the mean value of measuring for 5 times.Conversion formula is as described below.

H _0.4(％)＝H×0.4/d

Wherein,

H _0.4: 0.4mm thickness conversion haze value (%)

H: the measured value of the mist degree of sheet sample (%)

D: the sheet thickness of sample (mm) of mist degree determination part

(4) at least a direction in the face of sheet at 70 ℃ of 100% stress F when stretching down ₁₀₀

The system TENSILON UCT-100 of オ リ エ Application テ Star Network society that use has thermostatic bath carries out stress-deformation and measures under 70 ℃.With the strip of sample, measure the stress F when obtaining 70 ℃ of following leaf length directions 100% and stretching according to the method for JIS K-7127 defined along leaf length direction cut growth 200mm, wide 10mm ₁₀₀

Distance is 20mm between initial stage stretching chuck, and draw speed is 300mm/ minute.Change sample and carry out mensuration 20 times, use mean value.

(5) lactic acid oligomer becomes component (rac-Lactide amount)

Sheet is dissolved in the methylene dichloride, and adjustment concentration is 1g/20ml, adds acetone 60ml then, and then in ultrasonic stirring, drip hexanaphthene 320ml, make one-tenth fractional precipitation,, thereby make sample liquid this precipitate and separate, filtration based on polymer in poly lactic acid series.With this sample liquid use gas chromatograph 5890 types (Agilent Technologies society system, detector: the FID type), at post: DB-17MS type (J﹠amp; W society system), column temperature: analyze under 50～320 ℃, 25 ℃/minute, the condition of carrier gas: He, use the sample liquid of the lactide monomer that changes concentration to come the production standard curve in advance, obtain the rac-Lactide amount thus.

(6) layer thickness ratio

The sheet section is used ラ イ カ マ イ Network ロ シ ス テ system ズ (strain) system metalloscope LeicaDMLM, take pictures with 100 times of multiplying powers, transmitted light, thereby measure each layer thickness.

In addition as required, observe, make sheet add thermal crystallization and measure then for the section that carries out sheet easily.

(7) formability

On the vacuum forming machine with the bowl cover shape aluminium-making mould of diameter 95mm, high 7mm (50 ℃ of die temperatures) (becoming light industry (strain) system Off オ one ミ Application グ 300X type), place the sheet sample of the aliphatic polyester sheet of wide 210mm, long 300mm, thick 0.4mm, with being heated to 350 ℃ ceramic heater with sheet heating 15 seconds, vacuum was pushed 10 seconds and is obtained formed body on above-mentioned mould.

The formed body that range estimation obtains is estimated according to following benchmark.

Zero (very): the edge can be molded into the right angle

△ (can): the edge section has round a little partially

* (can not): significantly different with the shape of mould.

(8) thermotolerance

The formed body that uses the method by (7) to obtain is put into the distortion of baking oven after 2 hours that is set at 60 ℃ by visual assessment.

Zero (very): do not have distortion

△ (can): be out of shape little

* (can not): distortion is big.

(9) shock resistance

For length direction, the width of aliphatic polyester sheet, make respectively 20mm * 100mm rectangular sample each 10.To amount to 20 rectangular samples and form 180 ° of half such slow bendings,, judge according to following benchmark according to sample shape at this moment according to length 100mm.

Zero (very): 20 do not break (fractureing)

△ (can): the disruptive sample is not 1～19

* (can not): 20 all break.

(10) transparency

The haze value of the central authorities of the circular portion of the formed body that the method by (7) is obtained, use haze meter (Japanese electric look industry (strain) system NDH5000), per 1 level is carried out 5 times and is measured, mean value from 5 mensuration, obtaining as thickness is the haze value (%) of scaled value under the situation of 0.4mm, judges according to following benchmark according to this value.Conversion formula is as described below.

H _0.4(％)＝H×0.4/d

Wherein,

H _0.4: 0.4mm thickness conversion haze value (%)

H: the measured value of the mist degree of moulding sample (%)

D: the moulding thickness of sample (mm) of mist degree determination part

◎ (excellent): below 3%

Zero (very): greater than 3% and be below 5%

△ (can): greater than 5% and be below 10%

* (can not): greater than 10%

[aliphatic polyester resin]

Below, show the aliphatic polyester resin that uses among the embodiment.

P-1：

It is 190,000 poly (l-lactic acid) resin that the D-lactic acid units contains the proportional weight-average molecular weight that is 1 mole of %, PMMA convert.

P-2：

It is 190,000 poly (l-lactic acid) resin that the D-lactic acid units contains the proportional weight-average molecular weight that is 5 moles of %, PMMA convert.

P-3：

It is 190,000 poly (l-lactic acid) resin that the D-lactic acid units contains the proportional weight-average molecular weight that is 12 moles of %, PMMA convert.

P-4：

The mass ratio of P-1 and P-2 is 50: 50 a mixture.

P-5：

The mass ratio of P-1 and P-3 is 50: 50 a mixture.

P-6：

The weight-average molecular weight that P-1 and PMMA convert is that the mass ratio of 10,000 poly-D-lactic acid resin (the L-lactic acid units contains proportional 1 mole of %) is 90: 10 a mixture.

P-7：

It is 23.7 ten thousand poly (l-lactic acid) resin that the D-lactic acid units contains the proportional weight-average molecular weight that is 1.4 moles of %, PMMA convert.

P-8：

It is 11.8 ten thousand poly (l-lactic acid) resin that the D-lactic acid units contains the proportional weight-average molecular weight that is 1.4 moles of %, PMMA convert.

P-8：

It is 9.8 ten thousand poly (l-lactic acid) resin that the D-lactic acid units contains the proportional weight-average molecular weight that is 1.4 moles of %, PMMA convert.

[crystallization nucleating agent]

Below, show the crystallization nucleating agent that uses among the embodiment.

Q-1：

Ethylene laurylamide (EBLA)

Q-2：

Ethylene bis stearamide (EBSA)

Q-3：

Two (to the methyl benzylidene) Sorbitol Powder

Q-4：

Q-1 (30g) and Q-3 (30g) are added among dimethyl sulfoxide (DMSO) (DMSO) 200mL, and with system internal heating to 100 ℃, it is transparent to be stirred to solution becomes.DMSO is removed in underpressure distillation then, and then with dry 12 hours of 100 ℃ Vacuumdrier, thereby obtain solution mixture Q-4.

In addition, confirm Q-4's ¹H-NMR wave spectrum (DMSO solvent), the proton peak of the acid amides among near the Q-1 that the result observes 3.4ppm and monomer compare, to the about 0.03ppm of downfield displacement, in addition, the proton peak of the hydroxyl among near the Q-3 that observes 4.5ppm and monomer compare, to the about 0.05ppm of upfield shift.Hence one can see that, formed hydrogen bond among the Q-4 between ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder.

Q-5：

With Q-1 (30g) and Q-3 (30g) under nitrogen atmosphere, 300 ℃ of melting mixing 5 minutes, thereby obtain molten mixture Q-5.

In addition, confirm Q-5's ¹H-NMR wave spectrum (DMSO solvent), the proton peak of the acid amides among near the Q-1 that the result observes 3.4ppm and monomer compare, to the about 0.03ppm of downfield displacement, in addition, the proton peak of the hydroxyl among near the Q-3 that observes 4.5ppm and monomer compare, to the about 0.05ppm of upfield shift.Hence one can see that, formed hydrogen bond among the Q-5 between ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder.

[making of aliphatic polyester sheet]

(embodiment 1)

With aliphatic polyester resin (P-1), add the exhaust twin screw extruder at 98: 2 with mass ratio with the solution mixture (Q-4) of ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder, extrude with the T die orifice mould that die temperature is set at 200 ℃, by applying the electrostatic mode, make on its curtain coating rotary drum that sticks to 30 ℃ and cooling curing, thereby obtain omnidirectional cast sheet.

Next being heated to carrying this omnidirectional cast sheet on 120 ℃ the silicone roller, make that be 10 seconds duration of contact, then carrying and reduction sheet temperature on 30 ℃ cooling roller, thus obtain omnidirectional of thick 0.40mm.

The thermotolerance of the sheet that obtains, the transparency, shock resistance are good.

(embodiment 2～6, reference example 1～4)

It is such that aliphatic polyester resin, the crystallization nucleating agent that constitutes sheet become table 1-1,1-2 respectively, in addition, carries out similarly to Example 1.

(embodiment 7)

With aliphatic polyester resin (P-6), add the exhaust twin screw extruder at 98: 2 with mass ratio with the solution mixture (Q-4) of ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder, under 200 ℃, carry out melting mixing, extrude with the T die orifice mould that is cooled to 180 ℃ then, by applying the electrostatic mode, make on its curtain coating rotary drum that sticks to 30 ℃ and cooling curing, thereby obtain omnidirectional cast sheet.

Next being heated to carrying this omnidirectional cast sheet on 120 ℃ the silicone roller, make that be 10 seconds duration of contact, then carrying and reduction sheet temperature on 30 ℃ cooling roller, thus obtain omnidirectional of thick 0.40mm.

The thermotolerance of the sheet that obtains, the transparency, shock resistance are good.

(embodiment 8)

The resin of using as layer A, with aliphatic polyester resin (P-1), add the exhaust twin screw extruder with the solution mixture (Q-4) of ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder at 98: 2 with mass ratio, in addition, the resin of using as layer B, with aliphatic polyester resin (P-2), add other exhaust twin screw extruder at 98: 2 with mass ratio with the solution mixture (Q-4) of ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder, under 200 ℃, carry out melting mixing, carrying out compoundization then makes layer constitute A/B/A, carry out coextrusion with T die orifice mould, by applying the electrostatic mode, make on its curtain coating rotary drum that sticks to 30 ℃ and cooling curing, thereby obtain omnidirectional cast sheet.

Next being heated to carrying this omnidirectional cast sheet on 120 ℃ the silicone roller, make that be 10 seconds duration of contact, then carrying and reduction sheet temperature on 30 ℃ cooling roller, thus obtain omnidirectional of thick 0.40mm.

The formability of the sheet that obtains, thermotolerance, the transparency, shock resistance are good.

(embodiment 9)

The resin of using as layer A, with aliphatic polyester resin (P-1), add the exhaust twin screw extruder with the solution mixture (Q-4) of ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder at 98: 2 with mass ratio, in addition, the resin of using as layer B, with aliphatic polyester resin (P-2), add other exhaust twin screw extruder at 98: 2 with mass ratio with the solution mixture (Q-4) of ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder, under 200 ℃, carry out melting mixing, carrying out compoundization then makes layer constitute A/B/A, carry out coextrusion with T die orifice mould, by applying the electrostatic mode, make on its curtain coating rotary drum that sticks to 30 ℃ and cooling curing, thereby obtain omnidirectional cast sheet.

Next being heated to carrying this omnidirectional cast sheet on 120 ℃ the silicone roller, make that be 30 seconds duration of contact, then carrying and reduction sheet temperature on 30 ℃ cooling roller, thus obtain omnidirectional of thick 0.40mm.

Thermotolerance, the shock resistance of the sheet that obtains are good.

(embodiment 10)

The resin of using as layer A, with aliphatic polyester resin (P-6), add the exhaust twin screw extruder with the solution mixture (Q-4) of ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder at 98: 2 with mass ratio, in addition, the resin of using as layer B, with aliphatic polyester resin (P-2), add other exhaust twin screw extruder at 98: 2 with mass ratio with the solution mixture (Q-4) of ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder, under 200 ℃, carry out melting mixing, carrying out compoundization then makes layer constitute A/B/A, carry out coextrusion with the T die orifice mould that is cooled to 180 ℃, by applying the electrostatic mode, make on its curtain coating rotary drum that sticks to 30 ℃ and cooling curing, thereby obtain omnidirectional cast sheet.

Next being heated to carrying this omnidirectional cast sheet on 120 ℃ the silicone roller, make that be 10 seconds duration of contact, then carrying and reduction sheet temperature on 30 ℃ cooling roller, thus obtain omnidirectional of thick 0.40mm.

The formability of the sheet that obtains, thermotolerance, the transparency, shock resistance are good.

(embodiment 11)

With aliphatic polyester resin (P-1), add the exhaust twin screw extruder at 98: 2 with mass ratio with the solution mixture (Q-4) of ethylene laurylamide and two (to the methyl benzylidene) Sorbitol Powder, the T die orifice mould that is set at 200 ℃ with die temperature is extruded, by applying the electrostatic mode, make on its curtain coating rotary drum that sticks to 30 ℃ and cooling curing, thereby obtain omnidirectional cast sheet.

Next being heated to carrying this omnidirectional cast sheet on 120 ℃ the silicone roller, make that be 5 seconds duration of contact, then carrying and reduction sheet temperature on 30 ℃ cooling roller, thus obtain omnidirectional of thick 0.48mm.Should omnidirectional with the roll-type drawing machine along its length, stretch 1.1 times down for 90 ℃ in temperature.With the cooling temporarily on cooling roller of this uniaxial extension sheet, then with two ends with the clip clamping and import in the tenter machine, broad ways is in 1.1 times of the stretchings down of 95 ℃ of temperature.Next under the regular length condition, in 140 ℃ of thermal treatments of carrying out 10 seconds of temperature, broad ways is carried out 1% relaxation processes then, thereby obtains biaxially oriented of thick 0.4mm.

The thermotolerance of the sheet that obtains, the transparency, shock resistance are good.

(embodiment 12)

It is such that aliphatic polyester resin, the crystallization nucleating agent that constitutes sheet become table 1-2 respectively, in addition, carries out similarly to Example 7.

(reference example 5, embodiment 13)

It is such that aliphatic polyester resin, the crystallization nucleating agent that constitutes sheet become table 1-3 respectively, in addition, carries out similarly to Example 8.

(embodiment 14)

It is such that aliphatic polyester resin, the crystallization nucleating agent that constitutes sheet become table 1-3 respectively, in addition, carries out similarly to Example 10.

(reference example 6)

It is such that aliphatic polyester resin, the crystallization nucleating agent that constitutes sheet become table 1-3 respectively, in addition, carries out similarly to Example 11.

(comparative example 1)

Aliphatic polyester resin (P-1) is added the exhaust twin screw extruder, the T die orifice mould that is set at 200 ℃ with die temperature is extruded, by applying the electrostatic mode, make on its curtain coating rotary drum that sticks to 30 ℃ and cooling curing, thereby obtain the omnidirectional cast sheet of thick 0.40mm.

The degree of crystallinity of the sheet that obtains not within the scope of the invention, the thermotolerance of sheet is insufficient.

(comparative example 2)

The sheet of comparative example 1 gained is put into the hot-air oven 10 minutes that is set at 120 ℃.

The all mist degree of the sheet that obtains not within the scope of the invention, the thermotolerance of sheet, the transparency are insufficient.

(comparative example 3)

Aliphatic polyester resin (P-1) and ethylene laurylamide (Q-1) are added the exhaust twin screw extruder with mass ratio at 99: 1, the T die orifice mould that is set at 200 ℃ with die temperature is extruded, by applying the electrostatic mode, make on its curtain coating rotary drum that sticks to 30 ℃ and cooling curing, thereby obtain omnidirectional cast sheet.

Next being heated to carrying this omnidirectional cast sheet on 120 ℃ the silicone roller, make that be 60 seconds duration of contact, then carrying and reduction sheet temperature on 30 ℃ cooling roller, thus obtain omnidirectional of thick 0.40mm.

The degree of crystallinity of the sheet that obtains, whole mist degree not within the scope of the invention, the formability of sheet is insufficient.

(comparative example 4)

Aliphatic polyester resin (P-1) and ethylene laurylamide (Q-1) are added the exhaust twin screw extruder with mass ratio at 99: 1, the T die orifice mould that is set at 200 ℃ with die temperature is extruded, by applying the electrostatic mode, make on its curtain coating rotary drum that sticks to 30 ℃ and cooling curing, thereby obtain omnidirectional cast sheet.

Next being heated to carrying this omnidirectional cast sheet on 120 ℃ the silicone roller, make that be 40 seconds duration of contact, then carrying and reduction sheet temperature on 30 ℃ cooling roller, thus obtain omnidirectional of thick 0.40mm.

Whole mist degree of the sheet that obtains not within the scope of the invention, the formability of sheet is insufficient.

(embodiment 15)

Aliphatic polyester resin (P-7) usefulness Vacuumdrier is following dry 10 hours at 80 ℃.Should (P-7) and ethylene laurylamide (Q-1) add the exhaust twin screw extruder, the temperature of feed entrance point is 170 ℃, in 210 ℃ of following melting mixing of extrusion temperature, thereby obtains the master batch of (P-7)/(Q-1)=95/5 weight %.Similarly, also obtain the master batch of (P-7)/(Q-3)=95/5 weight %.

The usefulness Vacuumdrier is following dry 10 hours at 80 ℃ with these 2 kinds of master batches and (P-7), make that (P-7)/(Q-1)/(Q-3)=98/1/1 weight % adds single screw extrusion machine like that, the temperature of feed entrance point is 170 ℃, under 210 ℃ of extrusion temperatures, carry out melting mixing, extrude with T die orifice mould, between roller, push and obtain omnidirectional of thick 0.50mm.

The sheet that obtains is fixed in the metal system frame, uses the tunnel type baking oven that has travelling belt 110 ℃ of thermal treatments of carrying out 10 seconds, thereby obtain the thermal treatment sheet.

(embodiment 16)

Thermal treatment was carried out under 110 ℃ 20 seconds, in addition, carried out similarly to Example 15.

(embodiment 17)

Thermal treatment was carried out under 120 ℃ 10 seconds, in addition, carried out similarly to Example 15.

(embodiment 18)

Thermal treatment was carried out under 120 ℃ 20 seconds, in addition, carried out similarly to Example 15.

(embodiment 19)

Aliphatic polyester resin (P-7) usefulness Vacuumdrier is following dry 10 hours at 80 ℃.Make and (P-7) to add the exhaust twin screw extruder like that for (P-7)/(Q-1)/(Q-3)=100/1/1 weight part with ethylene laurylamide (Q-1), two (to the methyl benzylidene) Sorbitol Powder (Q-3), the temperature of feed entrance point is 170 ℃, under 210 ℃ of extrusion temperatures, carry out melting mixing, thereby obtain particle.

This particle usefulness Vacuumdrier was descended dry 10 hours at 80 ℃, under the condition of 200 ℃ of press temperatures, 3 minutes fusion times, 30 seconds dwell times, carry out sheetization, obtain the sheet of thick 0.50mm with the frozen water cooling with manual press.

The sheet that obtains is fixed in the metal system frame, under 120 ℃, carries out 20 seconds thermal treatment with the tunnel type baking oven that has travelling belt, thereby obtain the thermal treatment sheet.

(embodiment 20)

Make (P-7)/(Q-1)/(Q-3)=100/1/0.5 weight part, thermal treatment was carried out under 120 ℃ 60 seconds with hot air dryer, in addition, carried out similarly to Example 19.

(embodiment 21)

(P-7)/(Q-1)/(Q-3)=and the 100/0.3/0.1 weight part, the thickness of compressed tablet is 1mm, thermal treatment was carried out under 120 ℃ 60 seconds with hot air dryer, in addition, carried out similarly to Example 19.

(embodiment 22)

(P-8)/(Q-1) weight part/(Q-3)=100/1/1, the thickness of compressed tablet is 0.5mm, thermal treatment was carried out under 120 ℃ 60 seconds with hot air dryer, in addition, carried out similarly to Example 19.

[0163]

(embodiment 23)

(P-9)/(Q-1) weight part/(Q-3)=100/1/1, the thickness of compressed tablet is 0.5mm, thermal treatment was carried out under 120 ℃ 60 seconds with hot air dryer, in addition, carried out similarly to Example 19.

The results are shown in of above embodiment shown 1-1,1-2,1-3,1-4,1-5.

[table 1-1]

[table 1-2]

[table 1-3]

[table 1-4]

[table 1-5]

The industry utilizability

Aliphatic polyester sheet of the present invention can be applied to the suction of use in the demonstration package of commodity is used Mould packing and wait conformal utensil class, the displaying of food disc, Drink dispenser bottle, packed meal case, drink Material cup waits container class, the various industrial materials such as other various wrapping formed bodys, surfacing extensively General purposes.

Aliphatic polyester sheet of the present invention can be used the empty moulding of vacuum forming, Vacuum Pressure, plunger helps Molded, straight line moulding, free drawing (free drawing) moulding, plug ring moulding, skeleton forming Etc. the various methods of forming, has high-mouldability. In addition, particularly preferably in require heat resistance and the transparency, Use in the packaging material such as the various conformal utensil classes of impact resistance, container.

Claims (11)

1. an aliphatic polyester sheet has the layer A that comprises aliphatic polyester at least,

The degree of crystallinity χ of this layer A _ABe 3～60%,

The compound that this layer A contains crystallization nucleating agent and have hydrogen bonded with crystallization nucleating agent, whole mist degree are below 10%.

2. aliphatic polyester sheet according to claim 1 is characterized in that, the described layer A that comprises aliphatic polyester contains:

As crystallization nucleating agent be selected from aliphatics carboxylic acid amides and N-replace in the urea at least a kind and

As with crystallization nucleating agent have hydrogen bonded compound be selected from aliphatics alcohols, Sorbitol Powder based compound, amino acid and the polypeptide at least a kind.

3. aliphatic polyester sheet according to claim 1 is characterized in that described aliphatic polyester is a poly(lactic acid).

4. aliphatic polyester sheet according to claim 1 is characterized in that, has the layer B that comprises aliphatic polyester at least, the degree of crystallinity χ of described layer B _BSatisfy following relational expression,

χ _A＞χ _B。

5. aliphatic polyester sheet according to claim 3 is characterized in that, described poly(lactic acid) is formed by the mixture of poly (l-lactic acid) and poly-D-lactic acid.

6. aliphatic polyester sheet according to claim 4, the aliphatic polyester of described layer A and layer B is a poly(lactic acid),

Constitute containing proportional Da (mole %), satisfying following relational expression of D-lactic acid units in the poly (l-lactic acid) of described layer A with the proportional Db (mole %) that contains of D-lactic acid units in the poly (l-lactic acid) that constitutes described layer B,

Da＜Db。

7. aliphatic polyester sheet according to claim 1, the stress F when extending for 70 ℃ following 100% of a direction in the face of sheet at least ₁₀₀Be 1～10MPa.

8. aliphatic polyester sheet according to claim 5 is characterized in that, to become component be below the 0.3 quality % to contained lactic acid oligomer in the sheet.

9. aliphatic polyester sheet according to claim 1 is characterized in that, the crystalline size of described layer A is below the 500nm.

10. aliphatic polyester sheet according to claim 4 is characterized in that, the crystalline size of described layer B is below the 500nm.

11. a formed body is made of the described aliphatic polyester sheet of claim 1.