CN100439099C - Biodegradable layered sheet - Google Patents
Biodegradable layered sheet Download PDFInfo
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- CN100439099C CN100439099C CNB2004800281090A CN200480028109A CN100439099C CN 100439099 C CN100439099 C CN 100439099C CN B2004800281090 A CNB2004800281090 A CN B2004800281090A CN 200480028109 A CN200480028109 A CN 200480028109A CN 100439099 C CN100439099 C CN 100439099C
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Abstract
It is an object to provide a biodegradable laminated sheet which is high in heat resistance, impact resistance and strength when subjected to loads at high temperature, does not develop wrinkles called 'bridges', which can be easily deep-drawn or formed into blister articles, which are typically complicated in shape. The biodegradable sheet is a laminated sheet comprising at least two layers. Each of the layers forming the laminated sheet is a resin composition comprising 75 to 25% by mass of a polylactic acid resin, and 25 to 75% by mass of a polyester resin having a glass transition temperature not exceeding 0 degrees C and a melting point higher than the glass transition temperature of the polylactic acid resin, and not exceeding the melting point of the polylactic acid resin, based on 100 mass percent of the total amount of the polylactic acid resin and the polyester resin. The D-lactic acid content of the polylactic acid resin contained in one layer, and the D-lactic acid content of the polylactic acid resin in the other layer are determined to satisfy a predetermined relationship. The laminated sheet is subjected to crystallization treatment.
Description
Technical field
The present invention relates to biodegradable laminated plate,, reach the method for these goods of moulding by the goods that this laminated plate is made.
Background technology
Used plastics such as polyethylene, polypropylene, polyvinyl chloride, polystyrene and PET material as the dish of food containers (if any cup and dish), blister package thing (blister pack), hot filling containers, conveying electronic parts, conveyer belt (carrier tape) etc.
These plastic products usually with after promptly be dropped soon, and how to dispose them and nowadays become important problem as burning or landfill.In particular, these resins such as polyethylene, polypropylene and polystyrene have high heating value when burning, so often damage incinerator when it burns in incinerator.Produce pernicious gas during the polyvinyl chloride burning.If these plastic products of landfill, they often promptly fill up the landfill place in a short time, and this is because they decompose in natural environment hardly because of its chemical stability, thus semipermanent be kept in the soil.If be poured in the natural environment, they can damage view or destroy the growing environment of marine animal.
Therefore, in order to protect environment, researching and developing biodegradable material at present energetically.One of this biodegradable material is a polylactic resin.Because polylactic resin is biodegradable, thus its hydrolysis naturally in soil or water, and resolved into harmless material by microorganism.In addition, because its combustion heat is low, so even also do not damage incinerator when burning.And, because polylactic resin derives from plant, so it does not rely on one of natural resources that crude oil-expection will exhaustion.
But, because the polylactic resin hear resistance is low, the material of its container that is considered to be not suitable for use at high temperature using (as deposit the food that will heat or the container of boiling water).In addition, if polylactic resin plate or be stored in the warehouse or transported in truck or steamer by the goods that this plate is made, because the inside of these warehouses, truck or steamer for example generates heat to high temperature in summer, they often are out of shape or fusion each other.
From patent document 2, as can be known,, can improve hear resistance, impact resistance and the formability of the goods that form by this lamina by the lamina that pre-crystallization is made by the resin combination that comprises polylactic resin and polyester.
Patent document 1:JP 8-193165A
Patent document 2:JP 2003-147177A
Summary of the invention
The problem to be solved in the present invention
But in the method in front, because molded PLA crystallization in mould so molded polylactic resin must remain in the mould when crystallization, makes the molded period ratio cycle generally speaking to grow, this has increased production cost.Moreover, also additionally need the firing equipment of heating mould.
For the lamina of patent document 2,, then on goods, produce the wrinkle of so-called " bridge joint phenomenon " according to its shape if utilize combination die to form a plurality of goods by this lamina.Utilize vacuum forming machine by the goods of this plate formation of deep-draw or the bubble goods (blisterarticle) with complicated shape that formed by above-mentioned plate, the mouldability of this mechanograph worsens slightly.
The purpose of this invention is to provide a kind of biodegradable laminated plate, and the goods that utilize this biodegradable laminated plate to form, this laminated plate does not cause environmental problem, under high temperature load, still has high hear resistance, impact resistance and intensity, do not produce the wrinkle that is called " bridge joint phenomenon ", and easily deep-draw or be shaped to the bubble goods that have complicated shape usually.
Solve the method for described problem
According to the present invention, to achieve these goals, a kind of biodegradable laminated plate is provided, it comprises two-layer at least, described each two-layer at least layer comprises resin combination, this resin combination comprises the polylactic resin of 75～25% quality and the mylar of 25～75% quality, this mylar has and is no more than 0 ℃ glass transition temperature, and be higher than the glass transition temperature of polylactic resin but be no more than the fusing point of polylactic resin fusing point, the total amount of described polylactic resin and mylar is by 100% quality, wherein said two-layer at least in the polylactic resin that comprised of one deck D-lactic acid content Da (%) with described two-layer at least in the D-lactic acid content Db (%) of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
This laminated plate lives through crystallization and handles.
Advantage of the present invention
Because laminated plate of the present invention comprises polylactic resin and mylar, so it can not cause any environmental problem.
Because laminated plate of the present invention comprises that the D-lactic acid content is not more than 7% ground floor, and the D-lactic acid content is greater than the ground floor D-lactic acid content 3% or the higher second layer, so when this laminated plate crystallization, the ground floor that the D-lactic acid content is low is easier to crystallization than the second layer.Thereby laminated plate of the present invention not only is included in the layer of the preceding crystallization of moulding, and comprises the seldom layer of possibility crystallization.This has eliminated and has kept mold temperature to form laminated plate near the crystallization temperature (80～130 ℃) of polylactic resin to promote the needs of laminated plate crystallization, to make to utilize the mould that remains normal temperature in the normal moulding circulation.So the goods of moulding have enough hear resistances.
Because laminated plate of the present invention comprises the layer that is difficult to crystallization, so, the gentle brewage of the shell that has complicated shape usually can be formed by laminated plate of the present invention.
Laminated plate according to the present invention comprises the mylar with particular glass transition temperature (Tg) and fusing point, and has high hear resistance, impact resistance, formability and the intensity under high temperature load by the goods that this laminated plate forms.They also seldom produce the wrinkle of so-called " bridge joint phenomenon ".
Description of drawings
Fig. 1 is according to the typical relation figure between the dynamic viscoelastic of biodegradable laminated plate of the present invention and its temperature.
The specific embodiment
Biodegradable laminated plate according to the present invention comprises two-layer at least, and each layer comprises resin combination, and this resin combination comprises the mylar of polylactic resin and regulation.
Polylactic resin is the polymer that obtains for the monomer of its main component with lactic acid by polycondensation.There are two kinds of lactic acid, i.e. L-lactic acid and D-lactic acid, it is an optical isomer.Polylactic resin has different degree of crystallinity according to the ratio of these two kinds of lactic acid contents.Comprising ratio is 80: 20 to 20: 80 the L-lactic acid and the randomcopolymer of D-lactic acid, is the complete unbodied transparent polymer that does not have degree of crystallinity.Near its glass transition temperature 60 ℃ is softening.
Comprise ratio and be 100: 0 to 80: 20 or 20: 80 to 0: 100 L-lactic acid and the randomcopolymer of D-lactic acid have degree of crystallinity.Although its degree of crystallinity depends on the content ratio of L-lactic acid and D-lactic acid, the copolymer of its glass transition temperature and front is roughly the same, promptly about 60 ℃.Extrude this copolymer and cooling rapidly soon after melt is extruded by melt, it is transformed into the amorphous materials of highly transparent.Then, if cooling lentamente, then it is transformed into crystalline material.Homopolymers promptly only contains the polymer of L-lactic acid or D-lactic acid, is not less than 180 ℃ semi-crystalline polymer for fusing point.
Be used for polylactic resin of the present invention and can be containing L-lactic acid or D-lactic acid homopolymers, i.e. poly-(L-lactic acid) or poly-(D-lactic acid) for its construction unit; Contain L-lactic acid and D-lactic acid copolymer, i.e. poly-(DL-lactic acid) for its construction unit; Perhaps their mixture.It also can be the copolymer of aforementioned polymer and other hydroxycarboxylic acid or glycol/dicarboxylic acids.It can also comprise a spot of chain extender residue.
Polylactic resin can carry out polymerization by known method such as polycondensation or ring-opening polymerisation.In polycondensation, the PLA with required composition can obtain by directly making the polycondensation that stands to dewater of L-lactic acid, D-lactic acid or its mixture.
In ring-opening polymerisation (lactide method), PLA can be obtained by lactide, the cyclic dimer of lactic acid, can add the catalysts selective with polymerization regulating action when needing.
Aforementioned will can be the optical isomer (for example, the D-lactic acid when this lactic acid is L-lactic acid, and the L-lactic acid of this lactic acid when being D-lactic acid) of lactic acid with other hydroxycarboxylic acid of PLA copolymerization; The aliphatic hydroxyl carboxylic acid such as the glycolic acid of two functional groups, 3-hydroxybutyric acid, 4 hydroxybutyric acid, 2-hydroxyl n-butyric acie, 2-hydroxyl-3,3-acid dimethyl, 2-hydroxy-3-methyl butyric acid, 2-methyllactic acid and 2-hydroxycaproic acid; And lactone such as caprolactone, butyrolactone and valerolactone.
Above-mentionedly to can be ethylene glycol, 1,4-butanediol or 1,4-cyclohexanedimethanol with the aliphatic diol of polylactic acid polymer copolymerization.Aforementioned aliphatic dicarboxylic acid can be butanedioic acid, adipic acid, suberic acid, decanedioic acid or dodecanedioic acid.
In addition, as a spot of copolymerization component, can use the ethylene oxide adduct of non-aliphatic dicarboxylic acid such as terephthalic acid (TPA) and/or non-aliphatic diol such as bisphenol-A as required.
The weight average molecular weight that is used for polylactic resin of the present invention is preferably 60000～700000, and more preferably 80000～400000, be preferably 100000～300000 especially.If molecular weight is too little, then actual physical character such as mechanical strength and hear resistance almost do not improve.If too big, then melt viscosity raises in so much, to such an extent as to infringement formability and machinability.
The mylar of afore mentioned rules is meant the mylar with particular glass transition temperature (Tg) and fusing point.Preferred this mylar has and is no more than 0 ℃, more preferably no more than-20 ℃ glass transition temperatures (Tg).If it is glass transition temperature is higher than 0 ℃, then often insufficient to the improvement of impact resistance.
Preferred this mylar has the fusing point of the glass transition temperature (Tg) that is higher than the polylactic resin that is added, and more preferably has to be not less than 80 ℃ fusing point.If be lower than this scope, then the hear resistance of the goods that formed by this laminated plate may be insufficient.The upper limit of the fusing point of mylar is the fusing point of the polylactic resin that added.If be higher than the fusing point of the PLA that is added, the PLA crystallization that then made in the laminated plate before forming laminated plate to be comprised is meaningless, and the appearance problem relevant with rigidity and formability.Polylactic resin has 135～180 ℃ fusing point usually, although it is along with construction unit is the mixing ratio of L-lactic acid and D-lactic acid and changing.
Have the glass transition temperature of above-mentioned particular range and the mylar of fusing point by employing, resulting laminated plate and the goods that formed by this laminated plate will have improved hear resistance, impact resistance and formability.
This mylar also comprises biodegradable aliphatic polyester except polylactic resin.This biodegradable aliphatic polyester comprises, the aliphatic polyester that obtains by condensation polyhydroxycarboxyliacid acid, aliphatic diol and aliphatic dicarboxylic acid, the aliphatic-aromatic polyester that obtains by condensation aliphatic diol, aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the aliphatic polyester copolymer that obtains by aliphatic diol, aliphatic dicarboxylic acid and hydroxycarboxylic acid, the aliphatic polyester that ring-opening polymerisation by annular lactone obtains, synthetic aliphatic polyester, and biosynthetic aliphatic polyester in the bacterium.
Aforementioned polyhydroxycarboxyliacid acid comprises hydroxycarboxylic acid such as 3-hydroxybutyric acid, 4 hydroxybutyric acid, 2-hydroxyl n-butyric acie, 2-hydroxyl-3,3-acid dimethyl, 2-hydroxy-3-methyl butyric acid, 2-methyllactic acid, and the homopolymers and the copolymer of 2-hydroxycaproic acid.
Aforementioned aliphatic diol comprises ethylene glycol, 1, and the 4-butanediol, and 1, the 4-cyclohexanedimethanol.Aforementioned aliphatic dicarboxylic acid comprises butanedioic acid, adipic acid, suberic acid, decanedioic acid, and dodecanedioic acid.Aforementioned aromatic dicarboxylic acid comprises terephthalic acid (TPA) and M-phthalic acid.
The aliphatic polyester that obtains by this condensation aliphatic diol and aliphatic dicarboxylic acid, and, obtain by making at least a aforesaid compound carry out polycondensation by the aliphatic-aromatic polyester that condensation aliphatic diol, aliphatic dicarboxylic acid and aromatic dicarboxylic acid obtain.Then, by with for example isocyanate compound chain extension, obtain required polymer.
Aforementioned aliphatic polyester comprises poly-butanedioic acid second diester, poly-butanedioic acid fourth diester, poly-butanedioic acid-adipic acid fourth diester, and poly-butanedioic acid-carbonic acid fourth diester.Aforementioned aliphatic-aromatic polyester comprises poly-adipic acid-butylene terephthalate, and poly-butanedioic acid-adipic acid-butylene terephthalate.
The aliphatic diol and the aliphatic carboxylic acid that are used for the aliphatic polyester copolymer that obtains by aliphatic diol, aliphatic dicarboxylic acid and hydroxycarboxylic acid, can be above-mentioned those.And hydroxycarboxylic acid can also be a L-lactic acid, D-lactic acid, DL-lactic acid, glycolic acid, 3-hydroxybutyric acid, 4 hydroxybutyric acid, 2-hydroxyl-n-butyric acie, 2-hydroxyl-3,3-acid dimethyl, 2-hydroxy-3-methyl-butyric acid, 2-methyllactic acid, 2-hydroxycaproic acid etc.
Aforementioned aliphatic polyester copolymer comprises poly-butanedioic acid-lactic acid fourth diester and poly-butanedioic acid-adipic acid-lactic acid fourth diester.For its composition, aliphatic diol and aliphatic dicarboxylic acid are its key component but in this case.In other words, preferred aliphat glycol: aliphatic dicarboxylic acid: the ratio of hydroxycarboxylic acid is 30～49.99: 35～49.99: 30～0.02.
The above-mentioned aliphatic polyester that obtains by the annular lactone ring-opening polymerisation obtains by one or more cyclic monomers of polymerization such as 6-caprolactone, δ-Wu Neizhi, Beta-methyl-δ-Wu Neizhi.
Aforementioned synthetic aliphatic polyester comprises the copolymer of cyclic acid anhydride and ethylene oxide, as the copolymer of succinyl oxide and oxirane or expoxy propane.
Biosynthetic aliphatic polyester comprises such as the biosynthetic aliphatic polyester of effect that passes through acetyl coenzyme A in the alcaligenes eutrophus bacteriums such as (Alcaligeneseutrophus) in the aforementioned bacterium.Although this class aliphatic polyester mainly comprise Poly-(poly--3HB), but industrially can advantageously they and hydroxypentanoic acid (HV) be copolymerized into the copolymer (copolymer of hydroxybutyric acid and hydroxypentanoic acid) of poly-(3HB-CO-3HV), thereby improve its practicality in plastics.HV copolymerization ratio is preferably 0～40mol%.Replace hydroxypentanoic acid, they can with alkanoic acid such as 3-hydroxycaproic acid, 3-Hydroxyoctanoic acid or the copolymerization of 3-hydroxyl octadecanoid acid of long-chain.The copolymer of 3HB and 3-hydroxycaproic acid comprises the copolymer of hydroxybutyric acid and hydroxycaproic acid.
In above-mentioned resin combination, the mixing ratio (quality) of preferred polylactic resin and mylar is 75～25: 25～75, more preferably 65: 35 to 35: 65.If the content of polylactic resin is higher than 75% quality, then formability is poor, so general moulding such as vacuum forming or air-pressure forming difficulty.If less than 25% quality, then resulting sheet material and the goods that formed by this sheet material are poor rigidity often.
Only constitute according to resin combination of the present invention by polylactic resin and mylar.In other words, in fact polylactic resin content and mylar content sum are 100% quality.
Utilize this resin combination, preparation is according to biodegradable laminated plate of the present invention.This laminated plate should comprise multilayer such as two-layer, three layers or four layers.
If it is two-layer that biodegradable laminated plate according to the present invention comprises, then D-lactic acid content Da (%) and the Db (%) in the polylactic resin that comprised of each layer (ground floor and the second layer) should satisfy following relational expression (1):
Da≤7 and Db-Da＞3 (1)
Particularly, the D-lactic acid content (Da) in the polylactic acid polymer of formation ground floor should be not more than 7%, preferably is not more than 5%.If be higher than 7%, even then also often reduction of degree of crystallinity after crystallization is handled, this situation will be illustrated in the back.This can cause laminated plate rigidity deficiency when standing high temperature (for example 60～80 ℃) loading.In other words, as the polylactic resin that is comprised in the ground floor, preferably in handling, following crystallization can be easy to the material of crystallization.Preferred the following of Da value is limited to 0.5%.If be lower than 0.5%, then gained sheet material may be frangible.
D-lactic acid content (Db) the ratio content Da that is preferably formed in the polylactic acid polymer of the second layer is high more than 3%.If the difference of Db and Da is 3% or littler, the polylactic acid polymer that then forms the second layer has no practical significance at the polylactic acid polymer that all approaches to form ground floor aspect degree of crystallinity and the fusing point so form the sheet material of multilayer.
Biodegradable laminated plate according to the present invention stands crystallization to be handled.Crystallization is handled the crystallization that promotes specific polylactic resin.There is not concrete restriction to being used for crystallization processing of the present invention, as long as it promotes the crystallization of specific polylactic resin.For example, can adopt via the crystallization that heats.In handling via the crystallization of heating, sheet material can be heated to about 60～120 ℃ hot-rolling and contact several seconds to a few minutes, sheet material can heat preset time continuously by infrared heater or by hot-air, sheet material also can be in being heated to about 60～120 ℃ hot-air rolling and heating 0.5～72 hour.
After the crystallization, the polylactic resin that is comprised in the preferred ground floor has and is not less than 20% and be not more than 100% degree of crystallinity, more preferably has to be not less than 25% and be not more than 99% degree of crystallinity.If less than 20%, then can cause laminated plate rigidity deficiency when standing high temperature (for example 60～80 ℃) loading.The degree of crystallinity of the polylactic resin in the ground floor can be 100%.
After the crystallization, the polylactic resin that is comprised in the preferred second layer has and is not less than 0% and be not more than 20% degree of crystallinity, more preferably has to be not less than 1% and less than 15% degree of crystallinity.If greater than 20%, then formability is often insufficient, and often produces the wrinkle of so-called " bridge joint phenomenon ".The degree of crystallinity of the polylactic resin in the second layer can be 0%.
The polylactic resin that is contained in the ground floor or the second layer all can be the mixture of two or more dissimilar polylactic resin.In this case, no matter be content Da or content Db, it is the average D-lactic acid content in two or more polylactic resin.
Biodegradable laminated plate can be for double-layer structure, i.e. ground floor/second layer structure; For three-decker, i.e. ground floor/second layer/ground floor structure; Perhaps be structure more than four layers or four layers, as ground floor/second layer/ground floor ... / second layer structure, or ground floor/second layer/ground floor ... / ground floor structure.Preferred two skins are made of ground floor, and at least one internal layer is the second layer.If two skins constitute by ground floor, then two skins are high-crystallinity, so this biodegradable laminated plate has high-fire resistance and impact resistance, and have improved formability during moulding when it in vacuum forming machine or air-pressure forming machine.Between any ground floor and the second layer, can arrange and reclaim resin bed or the layer of performance between the ground floor and the second layer.
The gross thickness of preferred ground floor is 3～300 microns, more preferably 10～200 microns, and more preferably 30～100 microns.If less than 3 microns, can cause laminated plate rigidity deficiency when standing high temperature (for example 60～80 ℃) loading.If surpass 300 microns, formability may be insufficient.
Preparation method according to biodegradable laminated plate of the present invention now will be described.Each of plate layer can be formed by common forming method sheet material by above-mentioned resin combination.For example, each of plate layer can be by the formation of extruding in the T-die casting.But because polylactic resin has high-hygroscopicity and water-disintegrable, so need in preparation process, control moisture.Thereby if each layer is to utilize common single screw extrusion machine by extruding formation, then material should be used for example vacuum desiccator dehumidifying (drying).If use the discharge type double screw extruder to extrude, then can more effectively form each layer of plate, because this extruder can more effectively make material dehydration.
For each layer of laminated preparation thus without limits, as long as its not loss purpose of the present invention with the method that forms laminated plate.For example, this laminating method can be by choosing in four kinds of following methods.
(1) adopt two or more extruders, by each layer of branch manifold (multi-manifold) or feed sleeve pipe (feed block) type extruder head laminate, and the form of fusion sheet material is extruded.
(2) one of each layer of plate launched, and use resin as other layer by coating.
(3) after each layer with plate is heated to proper temperature, by hot pressing each layer combined by means of roller or press.
(4) by means of adhesive each is lumped together layer by layer.
The biodegradable laminate of Xing Chenging has excellent formability thus, does not have cross-over connection in the reality, and can form in the short period under the temperature that heating mould can not reach.
Particularly, can be shaped to required goods by any method in several different methods such as vacuum forming, air-pressure forming, vacuum pressure moulding and the compacting according to biodegradable laminated plate of the present invention.The forming temperature of preferred biodegradable laminated plate is not less than the fusing point of aforementioned mylar, but less than the fusing point that comprises polylactic resin in the ground floor.If forming temperature is less than the fusing point of mylar, then hear resistance and/or formability can be insufficient.If the fusing point of the polylactic resin that forming temperature is equal to or higher than in the ground floor to be comprised then can the appearance problem relevant with rigidity and formability.
Thereby, can under the temperature that is significantly less than the polylactic resin crystallization temperature, in short molding cycle, be shaped to required goods according to biodegradable laminated plate of the present invention.So, do not need mold heated to the crystallization temperature that approaches polylactic resin (as 80～130 ℃).The goods of Xing Chenging have high-fire resistance and impact resistance thus.The chances are for this because being contained in polylactic resin in the ground floor of the biodegradable laminated plate according to the present invention is partially crystallizable at least, but also may be because polylactic resin mix with other mylar, so have the viscoplasticity of uniqueness.
Fig. 1 shows the relation between dynamic viscoelastic according to biodegradable laminated plate of the present invention (E ') and its temperature.In Fig. 1, numeral＜1〉glass transition temperature (Tg) of expression polylactic resin, numeral＜2〉fusing point of expression mylar, and numeral＜3 expression is contained in the fusing point of the polylactic resin in the ground floor.
Biodegradable laminated plate can be＜1〉and＜3 between the temperature compacted under, but preferably＜2 and＜3 between the temperature compacted under.Because the polylactic resin that is comprised in the ground floor is handled partially crystallizable at least by crystallization, so resulting product has good hear resistance.
Biodegradable laminated plate according to the present invention can be shaped to following goods: lunch box, the dish of splendid attire food such as fish, meat, fruits and vegetables, bean curd, prepared food, dessert and the instant noodles and cup, the packing container of toothbrush, battery, medicine and cosmetics, the heat of pudding, jam and curry powder is filled (hot-fill) container, and transmits the dish and the carrier band (carrier tape) of electronic unit such as IC (integrated circuit), transistor and diode.
Can in forming, add additive to improve its performance according to the resin combination of biodegradable laminated plate of the present invention.This additive comprises stabilizing agent, antioxidant, and the UV absorbent, pigment, antistatic additive, conductive agent, releasing agent (release agent), plasticizer, flavor enhancement, antiseptic, nucleator reaches similar additive with it.
Embodiment
Now embodiments of the invention and Comparative Examples will be described.These examples do not limit the present invention in any way.The physical property of embodiments of the invention and Comparative Examples is measured and is estimated as follows.
[measure and estimate]
(1) hear resistance estimates 1
To utilize the goods of the punch moulding of diameter 75mm, degree of depth 50mm, draw ratio 0.67, by the hot air circulate baking oven 80 ℃ of following heat treatments 20 minutes.The volume slip is calculated as follows:
Volume slip (%)={ 1-(volume before the volume/moulded products heat treatment after the moulded products heat treatment) } * 100
The volume slip is good less than 3% goods, and the volume slip is not more than 6% goods and can uses in practice, and the volume slip can not use greater than 6% goods.
(2) hear resistance estimates 2
Utilize four goods of punch moulding of diameter 75mm, degree of depth 50mm, draw ratio 0.67, and water is filled.Then, seal its opening, it stacked mutually, and in the hot air circulate baking oven in 65 ℃ of following heat treatments 60 minutes.After the heat treatment, the observation goods see whether it is out of shape.
(3) impact resistance estimates 1
The water bullet shock machine that utilizes Toyo Seiki to make clashes into the water bullet of 0.5 inch of diameter against each biodegradable laminated plate sample with the speed of 3m/ second, and calculates and break up the required energy of laminated plate.
(4) impact resistance estimates 2
To fill water by the goods that each biodegradable laminated plate sample obtains, and, make its height fall on the concrete floor from 1 m with its opening sealing.Observe then to determine whether it breaks.
(5) measurement of glass transition temperature (Tg)
According to JIS-K-7121, measure the glass transition temperature of polyester with 10 ℃/minute firing rate by differential scanning calorimetry (DSC).
(6) measurement of crystallized temperature
According to JIS-K-7121, measure and to result from the melting heat (Δ Hm) and the crystallization heat (Δ Hc) of the polylactic resin in the biodegradable plate, and as follows according to the degree of crystallinity of these numerical computations polylactic resin:
Degree of crystallinity: χ c%=(Δ Hm-Δ Hc)/(content of polylactic resin in 92.8 * plate) * 100
(7) evaluation of formability
Utilize the punch (25 ℃ of mould temperature) of diameter 75mm, degree of depth 50mm, draw ratio 0.67, make the sheet material sample carry out vacuum forming (vacuum :-70cmHg).Observe the goods of moulding like this, to check its how moulding, whether to produce bridge joint and any other forming defect.The meaning of symbol is as follows in the table.
Zero: good moulding
△: in fact can accept
*: bad moulding
(8) overall assessment
In the table, hear resistance 1, hear resistance 2, impact resistance 1 and impact resistance 2 all with any sample of symbol zero, are all represented with symbol zero; Simultaneously to above-mentioned every all with symbol * any sample, all with symbol * expression.
(composition of polylactic resin in the laminated plate)
For the polylactic resin that forms each laminated plate sample, use Cargill Dow makes one of Nature Works level D-lactic acid of (seeing Table 1) or mixture, and is as shown in table 2.If the use mixture, then the D-lactic acid content in each rank D-lactic acid by the mean value of the D-lactic acid content of its mass fraction.
Table 1
Table 2
(embodiments of the invention 1)
Will as the resin in the table 2 of PLA 1 with as the PBS of biodegradable aliphatic polyester (poly-butanedioic acid fourth diester, Showa Highpolymer Co., Ltd makes: Bionolle 1001, fusing point: 111 ℃; Glass transition temperature :-40 ℃), the ratio in polylactic resin/biodegradable aliphatic polyester=50/50 (% quality) mixes.In this mixture of 100% quality, add of talcum (the Nippon Talc Co., Ltd manufacturing: Micro Ace L1) of 10% quality as inorganic filler, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 2)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=25/75 (% quality).In this mixture of 100% quality, add the talcum of 20% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=25/75 (% quality).In this mixture of 100% quality, add the talcum of 20% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 3)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=75/25 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=75/25 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 100: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 4)
Except using PBAT (poly-adipic acid-butylene terephthalate, BASF makes, Ecoflex, fusing point: 109 ℃, glass transition temperature :-30 ℃) as outside the biodegradable aliphatic polyester, obtaining thickness by the mode identical with embodiment 1 is 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 5)
Except using PBSL (poly-butanedioic acid-lactic acid fourth diester, Mitsubishi Chemical Corporation makes: AZ81T, the copolymer of 94% mole of butanedioic acid and 6% molar lactic acid, as acid constituents, fusing point: 110 ℃, glass transition temperature :-40 ℃) as outside the biodegradable aliphatic polyester, obtaining thickness by the mode identical with embodiment 1 is 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 6)
Except using PBSLA (poly-butanedioic acid-adipic acid-lactic acid fourth diester, Mitsubishi ChemicalCorporation makes: AD82W, the copolymer of 74% mole of butanedioic acid, 20% mole of adipic acid and 6% molar lactic acid, as acid constituents, fusing point: 87 ℃, glass transition temperature :-40 ℃) as outside the biodegradable aliphatic polyester, obtaining thickness by the mode identical with embodiment 1 is 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 7)
Except using PBSA (poly-butanedioic acid-adipic acid fourth diester, Showa Highpolymer Co., Ltd makes: Bionolle 3001, the copolymer of 85% mole of butanedioic acid and 15% mole of adipic acid, as acid constituents, fusing point: 93 ℃, glass transition temperature :-40 ℃) as outside the biodegradable aliphatic polyester, obtaining thickness by the mode identical with embodiment 1 is 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 8)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=25/75 (% quality).In this mixture of 100% quality, add the talcum of 20% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=25/75 (% quality).In this mixture of 100% quality, add the talcum of 20% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 1: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 400 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 9)
Will be as resin in the table 2 of PLA 2 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 115 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 10)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 3 (Db=7.1) and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 100 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 11)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and descend this mixture from the two-layer branch manifold extruder head of the parallel double-screw extruder of diameter 25mm at 220 ℃ as the aforementioned model of inorganic filler, extrude in the mode of anterior layer.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Because the biodegradable laminated plate of this embodiment has double-layer structure, so the back layer of this laminated plate is also served as in the intermediate layer.Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer and back layer is 2: 5.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 12)
Will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality as the aforementioned model of inorganic filler, and with this mixture under 220 ℃ from the branch manifold extruder head of the parallel double-screw extruder of diameter 40mm, extrude with the form of anterior layer and back layer.
In addition, will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and be the branch manifold extruder head of parallel double-screw extruder of 25mm from diameter this mixture as the aforementioned model of inorganic filler, extrude with the form in intermediate layer.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 3: 1: 3.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 13)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 40 ℃, obtain thickness and be 300 microns biodegradable laminated plate.The laminated plate of so preparation is rolled into the about 300 meters scroll of length.This scroll was heated 24 hours down in 75 ℃ in air oven.After the heat treatment, estimate this laminated plate in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 14)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=40/60 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will press polylactic resin/biodegradable aliphatic polyester=40/60 (% quality) as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester.In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 40 ℃, obtain thickness and be 300 microns biodegradable laminated plate.The laminated plate of so preparation is rolled into the about 300 meters scroll of length.This scroll was heated 24 hours down in 75 ℃ in air oven.After the heat treatment, estimate this laminated plate in a manner described.Evaluation result is shown in Table 4.
(Comparative Examples 1)
To 100% quality as the resin in the table 2 of PLA 1 in, add the talcum of 10% quality, and this mixture extruded from diameter is the individual layer extruder head of parallel double-screw extruder of 25mm under 220 ℃ as the aforementioned model of inorganic filler.The plate of so preparation is contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable plate.Estimate resulting plate in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 2)
To 100% quality as the resin in the table 2 of PLA 1 in, add the talcum of 10% quality, and this mixture extruded from diameter is the individual layer extruder head of parallel double-screw extruder of 25mm under 220 ℃ as the aforementioned model of inorganic filler.The plate of so preparation is contacted with the stack that remains 40 ℃, obtain thickness and be 300 microns biodegradable plate.Estimate resulting plate in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 3)
Will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=80/20 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and this mixture is extruded from diameter is the individual layer extruder head of parallel double-screw extruder of 25mm under 220 ℃ as the aforementioned model of inorganic filler.The plate of so preparation is contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable plate.Estimate resulting plate in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 4)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=80/20 (% quality).In this mixture of 100% quality, add the talcum of 10% quality as the aforementioned model of inorganic filler, and with this mixture under 220 ℃ from the branch manifold extruder head of the parallel double-screw extruder of diameter 20mm, extrude with the form of anterior layer and back layer.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=80/20 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 2: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 5)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=60/40 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and be to extrude the individual layer extruder head of parallel double-screw extruder of 25mm from diameter at 220 ℃ this mixture as the aforementioned model of inorganic filler.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate resulting plate in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 6)
Will be as resin in the table 2 of PLA 3 (Da=7.1) and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=60/40 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and under 220 ℃, be the branch manifold extruder head of parallel double-screw extruder of 25mm from diameter with this mixture as the aforementioned model of inorganic filler, extrude with the form of anterior layer and back layer.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=60/40 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 5.
Table 3
*1: ground floor; 2: the second layer
*The degree of crystallinity of the polylactic resin that is comprised wherein
Table 4
*1: ground floor; 2: the second layer
*The degree of crystallinity of the polylactic resin that is comprised wherein
Table 5
*1: ground floor; 2: the second layer
*The degree of crystallinity of the polylactic resin that is comprised wherein
[result]
From table 3 to table 5 as can be seen, the hear resistance of embodiments of the invention 1～14, impact resistance and formability all are excellent, and required goods can be formed by common moulding circulation by the laminated plate among any of these embodiment.
On the other hand, it is all poor aspect impact resistance and hear resistance not comprise the Comparative Examples 1 of any biodegradable aliphatic polyester.In addition, the formability extreme difference of goods in vacuum forming.The same with Comparative Examples 1, Comparative Examples 2 is also poor aspect hear resistance and impact resistance.Particularly about hear resistance 2, by the container generation shrinkage (buckling) of the sheet metal forming of Comparative Examples 2.
Poor heat resistance with Comparative Examples 3 of the biodegradable aliphatic polyester of low content.The same with Comparative Examples 2, about hear resistance 2, by the container generation shrinkage of the sheet metal forming of Comparative Examples 3.The hear resistance and the formability of Comparative Examples 4 are poor.Formability is also bad.
Comparative Examples 5 bridging occurs during the formability evaluation.The container that is formed by the plate of Comparative Examples 6 shrinkage occurs during hear resistance evaluation 2.
Claims (9)
1. biodegradable laminated plate; It comprises at least two-layer; Described every one deck at least two-layer all comprises resin combination; This resin combination comprises the polylactic resin of 75～25% quality and the mylar of 25～75% quality; Described mylar has and is no more than 0 ℃ glass transition temperature; And be higher than the glass transition temperature of described polylactic resin but be no more than the fusing point of described polylactic resin fusing point; The total amount of described polylactic resin and described mylar is by 100% quality
Wherein said two-layer at least in the D-lactic acid content Da% of the polylactic resin that comprised of one deck, with described two-layer at least in the D-lactic acid content Db% of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
Described laminated plate lives through crystallization and handles.
2. biodegradable laminated plate, it comprises two-layer at least, described each layer in two-layer at least all comprises resin combination, this resin combination comprises the polylactic resin of 75～25% quality and the mylar of 25～75% quality, described mylar has and is no more than 0 ℃ glass transition temperature, and being not less than 80 ℃ but be no more than the fusing point of described polylactic resin fusing point, the total amount of described polylactic resin and described mylar is by 100% quality
Wherein said two-layer at least in the D-lactic acid content Da% of the polylactic resin that comprised of one deck, with described two-layer at least in the D-lactic acid content Db% of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
Described laminated plate lives through crystallization and handles.
3. biodegradable laminated plate; It comprises at least two-layer; Described every one deck at least two-layer all comprises resin combination; This resin combination comprises the polylactic resin of 75～25% quality and the mylar of 25～75% quality; Described mylar has and is no more than 0 ℃ glass transition temperature; And be higher than the glass transition temperature of described polylactic resin but be no more than the fusing point of described polylactic resin fusing point; The total amount of described polylactic resin and described mylar is by 100% quality
Wherein said two-layer at least in the D-lactic acid content Da% of the polylactic resin that comprised of one deck, with described two-layer at least in the D-lactic acid content Db% of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
Described two-layer at least in the degree of crystallinity of the polylactic resin that comprised of one deck be not less than 20% but be not more than 100%, described two-layer at least in the degree of crystallinity of the polylactic resin that another layer comprised be not less than 0% but less than 20%.
4. biodegradable laminated plate, it comprises two-layer at least, described each layer in two-layer at least all comprises resin combination, this resin combination comprises the polylactic resin of 75～25% quality and the mylar of 25～75% quality, described mylar has and is no more than 0 ℃ glass transition temperature, and being not less than 80 ℃ but be no more than the fusing point of described polylactic resin fusing point, the total amount of described polylactic resin and described mylar is by 100% quality
Wherein said two-layer at least in the D-lactic acid content Da% of the polylactic resin that comprised of one deck, with described two-layer at least in the D-lactic acid content Db% of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
Described two-layer at least in the degree of crystallinity of the polylactic resin that comprised of one deck be not less than 20% but be not more than 100%, described two-layer at least in the degree of crystallinity of the polylactic resin that another layer comprised be not less than 0% but less than 20%.
5. according to each biodegradable laminated plate in the claim 1～4, wherein said one deck in two-layer at least has 3～300 microns thickness.
6. according to each biodegradable laminated plate in the claim 1～4, wherein said one deck in two-layer at least comprises two skins, and described another layer in two-layer at least is for being arranged in the one deck at least between described two skins.
7. according to the biodegradable laminated plate of claim 5, wherein said one deck in two-layer at least comprises two skins, and described another layer in two-layer at least is for being arranged in the one deck at least between described two skins.
8. goods, it is to obtain by each biodegradable laminated plate in the moulding claim 1～7, forming temperature be not less than mylar fusing point but less than described two-layer at least in the fusing point of the polylactic resin that comprised of one deck.
9. method by each biodegradable laminated plate moulded products in the claim 1～7, this method comprise make described laminated plate at the fusing point that is not less than mylar but less than described two-layer at least in the temperature compacted under of fusing point of the polylactic resin that one deck comprised.
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| CN101332691B (en) * | 2007-06-28 | 2012-06-20 | 伟盟工业股份有限公司 | Polylactic acid jointing plate and manufacture method thereof |
| WO2010072013A1 (en) * | 2008-12-25 | 2010-07-01 | 伟盟工业股份有限公司 | Polylactic acid bonding plate and manufacturing method thereof |
| CN101618565B (en) * | 2009-04-28 | 2011-02-02 | 王勇 | Manufacture method of environment-friendly wood substrate composite material |
| CN104401078B (en) * | 2014-12-17 | 2017-03-22 | 南通大学 | Multilayer polylactic acid composite plate and preparation method thereof |
| CN111941967B (en) * | 2020-09-04 | 2023-03-24 | 上海浦景化工技术股份有限公司 | Material and preparation method and application thereof |
| CN115403902B (en) * | 2022-09-27 | 2024-02-13 | 金发科技股份有限公司 | Biodegradable material and preparation method thereof |
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| US6372331B1 (en) * | 1998-06-03 | 2002-04-16 | Mitsubishi Plastics, Inc. | Biodegradable card |
| JP2002127343A (en) * | 2000-10-30 | 2002-05-08 | Mitsubishi Plastics Ind Ltd | Biodegradable thermoforming sheet-shaped material and container |
| JP2003170560A (en) * | 2001-12-06 | 2003-06-17 | Unitika Ltd | Polylactate biaxially stretched laminated film having heat sealability |
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| US6372331B1 (en) * | 1998-06-03 | 2002-04-16 | Mitsubishi Plastics, Inc. | Biodegradable card |
| JP2002127343A (en) * | 2000-10-30 | 2002-05-08 | Mitsubishi Plastics Ind Ltd | Biodegradable thermoforming sheet-shaped material and container |
| JP2003170560A (en) * | 2001-12-06 | 2003-06-17 | Unitika Ltd | Polylactate biaxially stretched laminated film having heat sealability |
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Address after: Tokyo, Japan Patentee after: MITSUBISHI CHEMICAL Corp. Address before: Tokyo, Japan Patentee before: MITSUBISHI RAYON Co.,Ltd. |
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Effective date of registration: 20170901 Address after: Tokyo, Japan Patentee after: MITSUBISHI RAYON Co.,Ltd. Address before: Tokyo, Japan Patentee before: MITSUBISHI PLASTICS, Inc. |