CN103087483B - Biaxial drawing polylactic acid sheet for card-based core layer and preparation method thereof - Google Patents
Biaxial drawing polylactic acid sheet for card-based core layer and preparation method thereof Download PDFInfo
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- CN103087483B CN103087483B CN201310006314.8A CN201310006314A CN103087483B CN 103087483 B CN103087483 B CN 103087483B CN 201310006314 A CN201310006314 A CN 201310006314A CN 103087483 B CN103087483 B CN 103087483B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of IC (integrated circuit) card making, and particularly relates to a biaxial drawing polylactic acid sheet for a card-based core layer and a preparation method thereof, aiming at overcoming the shortcomings of high brittleness, insufficient temperature resistance and bad hydrolysis resistance and aging resistance after long-time use of the existing PLA (polylactic acid) material applied to a card base. The invention provides a biaxial drawing polylactic acid sheet for a card-based core layer and a preparation method thereof by using a bio-degradable PLA sheet.
Description
Technical field
The invention belongs to IC-card and manufacture field, be specifically related to card base sandwich layer biaxial stretch-formed polylactic acid sheet material and preparation method.
Background technology
Smart card, also known as IC-card, refers to the card encapsulating integrated circuit (IC) chip wherein.IC-card has the features such as storage capacity is large, data security is high, antifalsification is good, application apparatus cost is low, technology maturation, is obtained for applies widely in every field such as finance, public security, traffic, communication, service, medical treatment.
Since IC-card is used for phonecard and achieves huge success by France in 1984, IC-card has obtained huge development.China started to start Golden Card Program in 1993, and technology and market is comparative maturity all.
The plastics sheet making IC-card is called card matrix material, and existing plastic clip sill has been widely used in the ID card, social security card, credit card, medical insurance card etc.Card matrix material mainly contains ABS (vinyl cyanide one divinyl one vinylbenzene), PVC (polyvinyl chloride), PET (polyethylene terephthalate), PC (polycarbonate), PETG (modified PET) etc.Current most popular card matrix material is PVC, but owing to containing chlorine element in PVC, the waste treatment of PVC card sill, buries or burn, be all unfavorable for environment protection.And be all be raw-material with oil with above-mentioned various card matrix materials, also there is the problem of lack of energy interior.
Therefore in order to solve above-mentioned environmental problem, bio-based degradable poly ester material is had an optimistic view of by industry in the application prospect of card matrix material.Polylactic resin is with the farm crop of the rich in starch such as corn for raw material, through modern biotechnology synthesizing lactic acid, then through special polymerization process generate macromolecular material.Poly(lactic acid) has Wholly-degradable, and place into the soil and can degrade for middle 6-12 month, polylactic acid article can be biodegradable into carbonic acid gas and water after a procedure.Therefore, poly(lactic acid) is the degradable biological environmental production material of a kind of energy truly.
Polylactic resin (PLA) has rigidity required by card matrix material, thermotolerance, printing, the even transparency, but the resin of PLA own is highly brittle, and the PLA elongation at break of the general trade mark is lower than 10%; Make cracky when sheet material bends, fracture, sheet material is in punching press, during embossing, easy to crack; Facile hydrolysis, the resistance to Long Service Life of PLA sheet material is not high; Applying on high temperature card base at some in addition, also there is the inadequate problem of Vicat softening point in PLA.
For above-mentioned actual application problem, the PLA resin as card base must carry out corresponding modification.Have patent EP0980894 to report the blend of PLA and poly butylene succinate to promote the mechanical property of PLA sheet material, but the toughness of the PLA blend thin films of this patent does not still have clear improvement, and on the contrary film tear strength be deteriorated.In JP 2004-155993 publication, disclose by adding the anti-hydrolytic performance that the aliphatic polycarbodiimide compound with isocyanic ester end improves PLA material in biodegradable plastic, but PLA material mechanical property does not promote significantly.
Summary of the invention
The present invention seeks to solve existing PLA material be applied on card base, there is fragility large, temperature tolerance is not high enough, life-time service hydrolysis, the defect that ageing-resistant performance performance is not good, utilizes biodegradable PLA sheet material, provides a kind of card base sandwich layer biaxial stretch-formed polylactic acid sheet material and preparation method thereof.
The technical scheme that the present invention takes is: the biaxial stretch-formed polylactic acid sheet material of a kind of card base sandwich layer, comprises following masses per-cent:
Described PLA resin comprises weight-average molecular weight at 10-50 ten thousand, and melting index is at 6-15g/10min, and fusing point is greater than 140 DEG C.
Described softening agent comprises tributyl citrate, tributyl acetylcitrate, one or more of polyoxyethylene glycol (molecular weight is at 2000-8000).
Described toughner comprises ethylene-octene copolymer, ethylene-acrylic acid copolymer, Styrene And Butyl-acrylate-acrylic terpolymer, maleic anhydride graft-ethylene-octene copolymer, butyleneglycol-hexanodioic acid-terephthaldehyde's acid copolymer, poly butylene succinate one or more.
Described nucleator comprise hydrazide kind compound, aryl amide compound, substituted aryl phosphates one or several.
Described hydrolysis properties-correcting agent comprises one or several of aliphatic polycarbodiimide compound of ethylene-ethylacrylate-glycidyl acrylate, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, isocyanic ester end.
Described lubricant comprise ethylene bis stearamide, amine hydroxybenzene, stearin, Zinic stearas one or several.
Described oxidation inhibitor comprises four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, one or several of three (nonyl phenyl) phosphorous acid ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
Described ultraviolet absorbers comprises Octabenzone, 2-(2 ,-hydroxy-5-methyl base phenyl) benzotriazole, 2,2-dihydroxyl-4,4-dimethoxy-benzophenones, double acid double phenol A ester one or several.
Described static inhibitor comprises ethoxylation oleyl amine.
A kind of card base sandwich layer preparation method of biaxial stretch-formed polylactic acid sheet material comprises the following steps:
A, drying: PLA resin and various additive are placed respectively in removal moisture drying tank at moderate temperatures and ensured that drying fully, stand-by;
B, make PLA master batch: first by dried PLA resin and toughner, lubricant, oxidation inhibitor, ultraviolet absorbers, titanium dioxide high-speed stirring fully after, enter the blended granulation of twin screw extruder, prilling temperature controls at 160-200 DEG C;
C, make formula particle: PLA resin quantitative with residue for the above-mentioned particle made, softening agent, nucleator, static inhibitor are mixed, enter twin screw extruder and carry out blended granulation, prilling temperature controls at 150-190 DEG C;
D, biaxial stretch-formed film forming: enter biaxial stretch-formed forcing machine after formula particle is carried out abundant drying and be filmed, extruder temperature controls at 150-200 DEG C;
E, slab: melt films cold drum of chilling between 15-50 DEG C cools, form diaphragm;
F, stretching film forming: diaphragm carries out first longitudinal stretching, preheating temperature controls at 40-90 DEG C, and draft temperature is set between 40-90 DEG C, and heat setting type is set between 20-90 DEG C, and draw ratio is 3-6 times; Then carry out cross directional stretch, preheating temperature is set in 40-120 DEG C, and draft temperature is set in 40-120 DEG C, and heat setting type is set between 50-160 DEG C, and draw ratio is 3-5 times;
G, by the sheet material produced through carrying out corona treatment, traction, rolling.
Advantage of the present invention is: adopt special PLA to fill a prescription modified system and select and biaxial stretch-formedly prepare card base sandwich layer PLA sheet material, thickness range is at 0.15mm-0.4mm, the elongation at break of obtained PLA sheet material, thermotolerance, anti-hydrolytic performance all have obvious lifting, in card base sandwich layer Application Areas, compare with the card matrix material not environmentally such as PVC, there is very strong competitive power, the card base fields such as the ID card, social security card, credit card, medical insurance card can be widely used in.
Embodiment
The biaxial stretch-formed polylactic acid sheet material of a kind of card base sandwich layer, comprises following masses per-cent:
Preparation method comprises the following steps:
A, drying: PLA resin and various additive are placed respectively in removal moisture drying tank at moderate temperatures and ensured that drying fully, stand-by;
B, make PLA master batch: first by dried PLA resin and toughner, lubricant, oxidation inhibitor, ultraviolet absorbers, titanium dioxide high-speed stirring fully after, enter the blended granulation of twin screw extruder, prilling temperature controls at 160-200 DEG C;
C, make formula particle: PLA resin quantitative with residue for the above-mentioned particle made, softening agent, nucleator, static inhibitor are mixed, enter twin screw extruder and carry out blended granulation, prilling temperature controls at 150-190 DEG C;
D, biaxial stretch-formed film forming: enter biaxial stretch-formed forcing machine after formula particle is carried out abundant drying and be filmed, extruder temperature controls at 150-200 DEG C;
E, slab: melt films cold drum of chilling between 15-50 DEG C cools, form diaphragm;
F, stretching film forming: diaphragm carries out first longitudinal stretching, preheating temperature controls at 40-90 DEG C, and draft temperature is set between 40-90 DEG C, and heat setting type is set between 20-90 DEG C, and draw ratio is 3-6 times; Then carry out cross directional stretch, preheating temperature is set in 40-120 DEG C, and draft temperature is set in 40-120 DEG C, and heat setting type is set between 50-160 DEG C, and draw ratio is 3-5 times;
G, by the sheet material produced through carrying out corona treatment, traction, rolling.
Use multiple embodiment below, adopt different components and consumption (wherein ratio is weight percentage), polylactic acid sheet material of the present invention and preparation method thereof is described.
Embodiment 1
In the present embodiment, that PLA resin is selected is MI=10g/10min, proportioning is 77%, tributyl citrate 3%, aryl amide compound 0.4%, ethylene-octene copolymer 2%, maleic anhydride graft-ethylene-octene copolymer 1%, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester 0.5%, ethylene bis stearamide 0.3%, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.3%, three (nonyl phenyl) phosphorous acid ester 0.1%, Octabenzone 0.4%, ethoxylation oleyl amine 0.2%, titanium dioxide 15%.
Card base biodegradable PLA sheet material of the present invention is according to component ratio proportioning each in embodiment, and be made according to above-mentioned preparation method, first time makes master batch temperature and controls at 160-200 DEG C, the extrusion temperature that secondary makes full formula particle controls at 170-190 DEG C, the masking temperature of particle controls at 160-200 DEG C, first longitudinal stretching, draft temperature is set between 40-90 DEG C, and draw ratio is 3.6 times; Then carry out cross directional stretch, draft temperature is set in 40-120 DEG C, and draw ratio is 4 times.
The said products is tested: tensile strength (ASTM D638) is 32MPa; Elongation at break (ASTM D638) is 130%; Vicat softening point (ASTM D648) is 85 DEG C.
Embodiment 2
In the present embodiment, that PLA resin is selected is MI=10g/10min, proportioning is 68%, tributyl citrate 4%, polyoxyethylene glycol 1%, hydrazide kind compound 3%, substituted aryl phosphate ester salt 0.7%, ethylene-acrylic acid copolymer 4%, ethylene-ethylacrylate-glycidyl 0.3%, the aliphatic polycarbodiimide 0.2% of isocyanic ester end, amine hydroxybenzene 0.2%, β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester 0.2%, tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester 0.2%, 2-(2,-hydroxy-5-methyl base phenyl) benzotriazole 0.2%.Octabenzone 0.4%, ethoxylation oleyl amine 0.1%, titanium dioxide 20%.
Card base biodegradable PLA sheet material of the present invention is according to component ratio proportioning each in embodiment, and be made according to above-mentioned preparation method, first time makes master batch temperature and controls at 160-190 DEG C, the extrusion temperature that secondary makes full formula particle controls at 160-190 DEG C, the masking temperature of particle controls at 160-200 DEG C, first longitudinal stretching, draft temperature is set between 50-80 DEG C, and draw ratio is 4 times; Then carry out cross directional stretch, draft temperature is set in 40-100 DEG C, and draw ratio is 3.8 times.
The said products is tested: tensile strength (ASTM D638) is 38MPa; Elongation at break (ASTM D638) is 150%; Vicat softening point (ASTM D648) is 82 DEG C.
Embodiment 3
In the present embodiment, that PLA resin is selected is MI=10g/10min, proportioning is 80%, tributyl acetylcitrate 3%, hydrazide kind compound 0.1%, Styrene And Butyl-acrylate-acrylic terpolymer 5%, ethylene-ethylacrylate-glycidyl 0.3%, the aliphatic polycarbodiimide 0.5% of isocyanic ester end, stearin 0.5%, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.1%.β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester 0.1%, 2,2-dihydroxyl-4,4-dimethoxy-benzophenone 0.3%, ethoxylation oleyl amine 0.4%, titanium dioxide 10%.
Card base biodegradable PLA sheet material of the present invention is according to component ratio proportioning each in embodiment, and be made according to above-mentioned preparation method, first time makes master batch temperature and controls at 180-200 DEG C, the extrusion temperature that secondary makes full formula particle controls at 160-190 DEG C, the masking temperature of particle controls at 160-200 DEG C, first longitudinal stretching, draft temperature is set between 40-80 DEG C, and draw ratio is 5 times; Then carry out cross directional stretch, draft temperature is set in 40-110 DEG C, and draw ratio is 4 times.
The said products is tested: tensile strength (ASTM D638) is 40MPa; Elongation at break (ASTM D638) is 140%; Vicat softening point (ASTM D648) is 80 DEG C.
Embodiment 4
In the present embodiment, that PLA resin is selected is MI=10g/10min, proportioning is 75%, polyoxyethylene glycol 5%, substituted aryl phosphate ester salt 0.1%, butyleneglycol-hexanodioic acid-terephthaldehyde's acid copolymer 2%, poly butylene succinate 1%, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester 0.2%, the aliphatic polycarbodiimide 0.5% of isocyanic ester end, amine hydroxybenzene 0.2%, Zinic stearas 0.1%, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.2%, three (nonyl phenyl) phosphorous acid ester 0.4%.Double acid double phenol A ester 0.1%.Ethoxylation oleyl amine 0.2%, titanium dioxide 15%.
Card base biodegradable PLA sheet material of the present invention is according to component ratio proportioning each in embodiment, and be made according to above-mentioned preparation method, first time makes master batch temperature and controls at 160-190 DEG C, the extrusion temperature that secondary makes full formula particle controls at 160-190 DEG C, the masking temperature of particle controls at 150-200 DEG C, first longitudinal stretching, draft temperature is set between 45-80 DEG C, and draw ratio is 6 times; Then carry out cross directional stretch, draft temperature is set in 50-100 DEG C, and draw ratio is 5 times.
The said products is tested: tensile strength (ASTM D638) is 36MPa; (ASTM D638 is 130 % to elongation at break; Vicat softening point (ASTM D648) is 84 DEG C.
Embodiment 5
In the present embodiment, that PLA resin is selected is MI=10g/10min, proportioning is 85%, tributyl citrate 2%, hydrazide kind compound 0.1%, Styrene And Butyl-acrylate-acrylic terpolymer 3%, the aliphatic polycarbodiimide 0.2% of isocyanic ester end, stearin 0.2%, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.1%, three (nonyl phenyl) phosphorous acid ester 0.1%.Octabenzone 0.1%.Ethoxylation oleyl amine 0.1%, titanium dioxide 9.1%.
Card base biodegradable PLA sheet material of the present invention is according to component ratio proportioning each in embodiment, and be made according to above-mentioned preparation method, first time makes master batch temperature and controls at 170-190 DEG C DEG C, the extrusion temperature that secondary makes full formula particle controls at 170-190 DEG C, the masking temperature of particle controls at 160-190 DEG C, first longitudinal stretching, draft temperature is set between 50-70 DEG C, and draw ratio is 5.2 times; Then carry out cross directional stretch, draft temperature is set in 55-98 DEG C, and draw ratio is 4.5 times.
The said products is tested: tensile strength (ASTM D638) is 41MPa; (ASTM D638 is 157 % to elongation at break; Vicat softening point (ASTM D648) is 82 DEG C.
Embodiment 6
In the present embodiment, that PLA resin is selected is MI=10g/10min, and proportioning is 65%, tributyl citrate 1%, tributyl acetylcitrate 1%.Polyoxyethylene glycol 1%, aryl amide compound 0.2%, maleic anhydride graft-ethylene-octene copolymer 10%, ethylene-ethylacrylate-glycidyl 0.2%, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester 0.1%, ethylene bis stearamide 0.1%, Zinic stearas 0.1%, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.1%, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester 0.2%.2-(2 ,-hydroxy-5-methyl base phenyl) benzotriazole 0.5%.Ethoxylation oleyl amine 0.5%, titanium dioxide 20%.
Card base biodegradable PLA sheet material of the present invention is according to component ratio proportioning each in embodiment, and be made according to above-mentioned preparation method, first time makes master batch temperature and controls at 150-190 DEG C, the extrusion temperature that secondary makes full formula particle controls at 160-190 DEG C, the masking temperature of particle controls at 160-190 DEG C, first longitudinal stretching, draft temperature is set between 50-90 DEG C, and draw ratio is 3.4 times; Then carry out cross directional stretch, draft temperature is set in 50-120 DEG C, and draw ratio is 5 times.
The said products is tested: tensile strength (ASTM D638) is 35MPa; (ASTM D638 is 160% to elongation at break; Vicat softening point (ASTM D648) is 81 DEG C.
Should be appreciated that embodiment described above only for explaining the present invention, being not intended to limit the present invention.Still be among protection scope of the present invention by spirit institute's apparent change of extending out of the present invention or change.
Claims (9)
1. a card base sandwich layer preparation method for biaxial stretch-formed polylactic acid sheet material, comprises following masses per-cent, and each component sum is 100%,
Preparation process is as follows:
A, drying: PLA resin and various additive are placed respectively in removal moisture drying tank at moderate temperatures and ensured that drying fully, stand-by;
B, make PLA master batch: first by dried PLA resin and toughner, lubricant, oxidation inhibitor, ultraviolet absorbers, titanium dioxide high-speed stirring fully after, enter the blended granulation of twin screw extruder, prilling temperature controls at 160-200 DEG C;
C, make formula particle: PLA resin quantitative with residue for the above-mentioned particle made, softening agent, nucleator, static inhibitor are mixed, enter twin screw extruder and carry out blended granulation, prilling temperature controls at 150-190 DEG C;
D, biaxial stretch-formed film forming: enter biaxial stretch-formed forcing machine after formula particle is carried out abundant drying and be filmed, extruder temperature controls at 150-200 DEG C;
E, slab: melt films cold drum of chilling between 15-50 DEG C cools, form diaphragm;
F, stretching film forming: diaphragm carries out first longitudinal stretching, preheating temperature controls at 40-90 DEG C, and draft temperature is set between 40-90 DEG C, and heat setting type is set between 20-90 DEG C, and draw ratio is 3-6 times; Then carry out cross directional stretch, preheating temperature is set in 40-120 DEG C, and draft temperature is set in 40-120 DEG C, and heat setting type is set between 50-160 DEG C, and draw ratio is 3-5 times;
G, by the sheet material produced through carrying out corona treatment, traction, rolling.
2. a kind of card base sandwich layer preparation method of biaxial stretch-formed polylactic acid sheet material according to claim 1, it is characterized in that: described PLA resin comprises weight-average molecular weight at 10-50 ten thousand, melting index is at 6-15g/10min, and fusing point is greater than 140 DEG C.
3. a kind of card base sandwich layer preparation method of biaxial stretch-formed polylactic acid sheet material according to claim 1, it is characterized in that: described softening agent comprises one or more in tributyl citrate, tributyl acetylcitrate, polyoxyethylene glycol, described molecular weight polyethylene glycol is between 2000-8000.
4. a kind of card base sandwich layer preparation method of biaxial stretch-formed polylactic acid sheet material according to claim 1, is characterized in that: described toughner comprise in ethylene-octene copolymer, ethylene-acrylic acid copolymer, Styrene And Butyl-acrylate-acrylic terpolymer, maleic anhydride graft-ethylene-octene copolymer, butyleneglycol-hexanodioic acid-terephthaldehyde's acid copolymer, poly butylene succinate one or several.
5. a kind of card base sandwich layer preparation method of biaxial stretch-formed polylactic acid sheet material according to claim 1, is characterized in that: described nucleator comprise in hydrazide kind compound, aryl amide compound, substituted aryl phosphates one or several.
6. a kind of card base sandwich layer preparation method of biaxial stretch-formed polylactic acid sheet material according to claim 1, is characterized in that: described hydrolysis properties-correcting agent comprise in the aliphatic polycarbodiimide compound of ethylene-ethylacrylate-glycidyl acrylate, sec.-propyl three (dioctyl phosphoric acid acyloxy) titanic acid ester, isocyanic ester end one or several.
7. a kind of card base sandwich layer preparation method of biaxial stretch-formed polylactic acid sheet material according to claim 1, is characterized in that: described lubricant comprise in ethylene bis stearamide, amine hydroxybenzene, stearin, Zinic stearas one or several.
8. a kind of card base sandwich layer preparation method of biaxial stretch-formed polylactic acid sheet material according to claim 1, it is characterized in that: described oxidation inhibitor comprises four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, three (nonyl phenyl) phosphorous acid ester, one or several in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
9. a kind of card base sandwich layer preparation method of biaxial stretch-formed polylactic acid sheet material according to claim 1, it is characterized in that: ultraviolet absorbers comprises Octabenzone, 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2,2-dihydroxyl-4, one or several in 4-dimethoxy-benzophenone, double acid double phenol A ester, described static inhibitor comprises ethoxylation oleyl amine.
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| CN104530667A (en) * | 2014-12-08 | 2015-04-22 | 安徽聚美生物科技有限公司 | PLA toughening material, PLA toughening plastic-suction sheet and preparation methods of two |
| CN105733214A (en) * | 2014-12-10 | 2016-07-06 | 黑龙江鑫达企业集团有限公司 | Method for preparing shock-resistant and deformation-resistant modified polylactic-acid material |
| CN104672826A (en) * | 2015-02-10 | 2015-06-03 | 利丰新材料科技（深圳）有限公司 | 3D printed PLA consumable and preparation method thereof |
| CN104817834A (en) * | 2015-05-18 | 2015-08-05 | 哈尔滨盛洋塑胶材料有限公司 | PLA (polylactic acid) resin toughening-modified material and preparation method thereof |
| CN106883569A (en) * | 2017-03-22 | 2017-06-23 | 金旸（厦门）新材料科技有限公司 | A kind of modified PLA of heat-resisting low warpage high and preparation method thereof |
| CN114108116B (en) * | 2021-11-18 | 2023-11-28 | 浙江正堂实业股份有限公司 | Rice-shaped polyester-nylon composite yarn and preparation process thereof |
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| CN100465227C (en) * | 2005-10-21 | 2009-03-04 | 中国科学院长春应用化学研究所 | Process for preparing ternary built completely biological degradation polylactic acid type composite material |
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