WO2007147290A1

WO2007147290A1 - Biodegrable grating sheet and its article, and preparing method thereof

Info

Publication number: WO2007147290A1
Application number: PCT/CN2006/001646
Authority: WO
Inventors: Yaobang Zou; Xiang Su; Xiaobo Mou; Liquan Zhou; Wenji Yu
Original assignee: Sichuan Yibin Wuliangye Group Co., Ltd.
Priority date: 2006-06-15
Filing date: 2006-07-11
Publication date: 2007-12-27
Also published as: CN1866052A; CN100417953C

Abstract

The present invention provides a biodegrable grating sheet and its article, and preparing method thereof which comprises the following steps: 1) the biodegrable polymer or the modified substance thereof is dried under the temprature of 50-120°C ; 2) the dried biodegrable polymer or the modified substance thereof is extruded to form a sheet by the extruder under the temprature of 120-250°C ,and there are uniform lens arrays with the same surface curvature on the front face of the sheet which becomes the biodegrable grating sheet after being cooled and shaped. The method for preparing the biodegrable article with stereo images comprises the following steps: 1) the grating sheet with stereo vision images is made of the biodegrable grating sheet ; 2) the article with stereo images is manufactured. The biodegrable grating sheet and the article thereof according to the present invention can be decomposed thoroughly to become water and carbon dioxide which are not harmful to the environment, in the air.

Description

Biodegradable grating sheet and article and manufacturing method thereof

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a lenticular sheet and article and a method of manufacturing the same, and more particularly to a plasmonic sheet and article which can be biodegraded and a method of manufacturing the same.

Background technique

At present, there are many lenticular sheets and their products, but they are generally prepared by using petroleum-based chemical materials. The grating products cannot be biodegraded after use, thereby causing great pollution to the environment.

Summary of the invention

In view of the deficiencies of the prior art, the technical problem to be solved by the present invention is to provide a biodegradable grating sheet and an article thereof, which are biodegradable.

The present invention also provides a method of producing the above biodegradable lenticular sheet and articles thereof.

The technical solution adopted by the present invention to solve the technical problem is: a biodegradable grating sheet made of a biodegradable polymer or a modified product thereof.

Further, the biodegradable polymer is a synthetic biodegradable polymer or a naturally biodegradable polymer.

Further, the modified product is a biodegradable nanocomposite formed by nano-silica, nano-montmorillonite or nano-hydroxy calcium phosphate modified by a composite method, a polymerization method or a direct dispersion method.

Further, the modified product is a biodegradable polymer formed by chain extension of a highly reactive isocyanate, a difunctional epoxy, a dioxazoline, a dibasic anhydride or a dialdehyde.

A method of making a biodegradable lenticular sheet comprising the steps of: 1) drying the biodegradable polymer or its modification at 50-120 ° C; 2) passing the extruder at 120-250 ° C Squeezed into a sheet having a lens array having the same uniform surface curvature on the front side of the sheet, which is cooled and shaped to become a biodegradable grating sheet.

Further, the grating sheet is made of a biodegradable polymer or a modification thereof. Further, the biodegradable polymer is a synthetic biodegradable polymer or a naturally biodegradable polymer.

Further, the modified product is a biodegradable nanocomposite formed by nano-silica, nano-montmorillonite or nano-hydroxy calcium phosphate by a composite method, a polymerization method or a direct dispersion method.

Confirmation Material.

A method of making a biodegradable stereographic article comprising the steps of: 1) forming a raster sheet of biodegradable material into a lenticular sheet having a stereoscopic image; and 2) producing a product having a stereoscopic image.

Further, step 1 is to print the pattern on the back plane of the biodegradable lenticular sheet. Further, step 1 is to apply a biodegradable protective glue or hot melt adhesive after printing the pattern on the back plane of the biodegradable grating sheet.

Further, step 1 is to composite the pattern with the biodegradable substrate after printing the pattern on the back plane of the biodegradable grating sheet.

Further, in step 1, after the pattern is printed on the back plane of the biodegradable grating sheet, the information carrier is placed on the grating sheet and then composited with the biodegradable substrate.

Further, step 1 is to print the pattern on the back plane of the biodegradable lenticular sheet, and then apply or print a biodegradable protective glue or hot melt adhesive to bond with the biodegradable substrate.

Further, step 1 is a composite of a biodegradable lenticular sheet after printing a pattern on the biodegradable substrate.

Further, in step 1, after the pattern is printed on the biodegradable substrate, the information carrier is placed on the substrate and then composited with the biodegradable grating sheet.

Further, step 1 is a method of printing a pattern on a biodegradable substrate, and then coating or printing a biodegradable protective or hot melt adhesive to be combined with the biodegradable grating sheet.

Further, the protective glue is an aliphatic polyester or an aliphatic polyester amide, and the hot melt adhesive is an aliphatic polyester, an aliphatic copolyamide or an aliphatic polyester amide.

Further, the biodegradable substrate is paper, leather, cotton, silk, biodegradable nonwoven, biodegradable plastic or wood.

Further, step 2 is to make a product with a stereoscopic image after punching.

Further, in step 2, after punching, the pattern or the text is stenciled to form a product with a stereoscopic image.

Further, the step 2 is punched and put into a mold, and is molded by an injection molding machine, an extrusion blow molding machine, a molding machine, a hot press or a laminating machine, and is taken out from the mold after cooling and hardening. Like a product.

The invention has the beneficial effects that: the biodegradable grating sheet of the invention and the product thereof are made of a biodegradable polymer or a modified product thereof, and can be completely decomposed into water and carbon dioxide under the action of microorganisms in nature, thus The environment is not harmful, overcoming the biggest drawback of the current preparation of grating sheets from petroleum-based chemical materials.

detailed description

The material of biodegradable lenticular sheet should be considered when considering the transparency, brittleness and processability of the material. The following two parts of natural and synthetic biodegradable polymers are used to describe the use as a degradable lenticular sheet. The polymer of the product.

(i) Natural biodegradable polymers

1. Natural microbial polyester: mainly polyhydroxyalkanoic acid (polyhydroxyalkanoic acid or polyhydroxyalkanoates, PHA), including from 3-light-based butyric acid

(3-hydroxybutyrate, HB or 3HB) synthesized poly-hydroxybutyric acid (polyhydroxybutyric acid or olyhydroxybutyrate, simvain or Ρ3ΗΒ), 3ΗΒ and 3-hydroxyvaleric acid (HV or 3HV) Polyester (PHBV, abbreviated as P (3HB-co-3HV)), and P(3HB-co-4HB) synthesized by copolymerization of 3HB and 4HB (4-hydroxybutyrate).

The brittleness and high price of natural microbial polyester can be solved by blending with other polymers. When blending and modifying, attention should be paid to the effect on transparency. The basic principle of blending is similar compatibility in molecular structure, for example with poly (vinyl acetate-co-vinyl alcohol), polymethyl propyl; 1; methyl citrate, poly (vinyl phenol), biodegradable polymerization Such as copolymerized PHB, polyethylene oxide (PE0), polycaprolactone (PCL), polylactic acid (PLA), cellulose, polyvinyl alcohol (PVA), chitin/chitosan and other aliphatic polyesters . If the molecular structure is incompatible, the product is opaque and cannot be used as a lenticular sheet. When the compatibility is poor, the transparency of the product is not good, and the lenticular sheet produced is inferior, and the improvement method can be added with a compatibilizer. Plasticizers such as liquid fatty acid esters, cyclic polyesters and the like can also be used for the improvement of the brittleness.

2. Natural bio-polysaccharides: such as starch, cellulose, chitosan, etc., although biodegradable, they must be converted into other derivatives to have processability, and transparency is also a problem. There are still many difficulties as grating sheets. .

(ii) Synthetic biodegradable polymers

Compared with natural materials, synthetic materials have the advantages of rich raw materials, adjustable structure and properties. Polymers useful as biodegradable lenticular sheets include the following categories:

1. Polyester: Polylactic acid (PLA), polycaprolactone (PCL), polyglycolic acid (also known as polyglycolide, PGA).

Polyglycolic acid (PGA): PGA is formed by ring-opening polymerization of glycolide, which produces hydroxy group B after degradation.

^A polylactic acid (PLA): PLA is formed by ring-opening polymerization of lactide. 5%。 The lactic acid obtained by the fermentation, L type accounted for 99.5 %, D type accounted for 0.5%. Its dimer can be controlled to convert to L, L, D, D and meso-lactide. The lactide-converted lactide, after purification, can be ring-opened to form polylactic acid. The L-type lactide polymerization product is a crystalline polylactic acid, and the polymer having a D-type content of > 15% is amorphous. The stereoplastic polylactic acid PLLA can be extruded into a film like other thermoplastic polyesters. Since the asymmetric carbon chain in the PLLA molecule has a regular configuration, it is a semi-crystalline polymer with a melting point of about 185 ° C and excellent mechanical properties, but the degradation time is very long. The copolymerized polylactic acid PDLLA, whose molecular structure is destroyed, is an amorphous polymer with a rapid degradation rate. When the polylactic acid is at room temperature, neutral and without enzyme, as long as the humidity is suitable, the degradation rate is fast, but when the molecular weight is high, it cannot be degraded by the enzyme, and only when the molecular weight is as low as tens of thousands or less.

Polycaprolactone (PCL): PCL is a cyclically polymerized ε-caprolactone. It is a semi-crystalline polymer with a crystallinity of about 45% and biodegradability. It has an ultra-low glass transition temperature (-62"C) and a low melting point (57 °C). It is in a rubbery state at room temperature, so it is difficult to use as a material for lenticular sheet without modification. The method of copolymerizing an ester with lactic acid or the like or introducing other monomers to block and graft to improve biodegradability and mechanical properties.

Other aliphatic polyesters synthesized from dibasic acids and ethylene glycol are tough, flexible, and insoluble in liquids and fully biodegradable.

The performance of the homopolyaliphatic polyester is not ideal, and the introduction of other monomers for block and grafting can be improved. Taking ΡΗΑ as an example, the introduction of 10 mol % of 15- pentadecanolide or ll-oxa-16- hexadecanolide resulted in a significant increase in elongation at break. The degradation rate of linear polyester can not be controlled, and the degradation rate can be controlled after functionalization, and has desirable properties such as hydrophilicity and biodegradability. The modified polyester can be used as a biodegradable lenticular sheet and article, and its degradation rate can be regulated by molecular structure design.

The aliphatic polyester has poor heat resistance during processing, and a method for effectively improving heat resistance and mechanical properties is to introduce an aromatic ester chain in its chain. An aliphatic polyester having a pendant aromatic group different from a polymer having an aromatic chain in the main chain, which combines the mechanical properties of an aromatic polymer with an aliphatic polymer. Biodegradability, can be used as biodegradable lenticular sheets and articles. However, as the content of the aromatic chain increases, as the molecular weight and crystallinity decrease, the elongation at break and the tear strength also decrease.

2. Polymers containing ester bonds and heteroatoms in the main chain

Polyanhydride: A polyanhydride formed by copolymerization of an aromatic anhydride with an aliphatic acid anhydride. The performance is between two homopolymers. By adjusting the ratio of the two, the degradation rate can be controlled.

Polyesteramide: Aliphatic polyester amide is a semi-crystalline polymer that can be completely decomposed under anaerobic conditions to produce carbon dioxide, biomass and water. Its physical properties are comparable to those of low-density polyethylene and can be extruded on general-purpose equipment. A biodegradable grating sheet is produced. Compared with aliphatic polyesters, aliphatic polyester amides have higher thermal stability, modulus and tensile strength. Due to the fragile ester bond in the main chain, the crystallinity is also lowered, because the hydrogen bond or the methylene group ratio is higher, and the degradation rate is slower than other aliphatic polyesters. The aliphatic polyester amide has a decomposition temperature higher than the melting point and can be melt processed, and the exchange reaction between the amide bond and the ester bond does not occur during the process.

Aliphatic polycarbonates and polyether esters: Since polyethylene glycol (PEG) is biodegradable, ring-opening polymerization of PEG and caprolactone can be used to obtain a polyether ester.

3. Biodegradable polymer with main chain containing heteroatoms and no ester bond

Amino acid polymer: α-amino acid is a natural product. The polyamino acid synthesized by it is a biodegradable, biocompatible non-toxic substance. It is synthesized by ring-opening polymerization and can be grafted or blocked with other monomers. In recent years, breakthroughs have been made in the synthesis of polyamino acids with natural polypeptide sequences.

Since the biodegradable polymer is generally an amorphous or semi-crystalline polymer, the strength is not high, and therefore its strength must be increased while maintaining its degradation characteristics. The present invention employs two methods to increase the strength: 1) Add nano-powder materials, such as: nano-silica, nano-montmorillonite or nano-hydroxy calcium phosphate. Because the size of the nanomaterial (l-50nm) is similar to the typical polymer chain length, the nanomaterial acts as a chain entanglement in the polymer matrix, similar to a physical cross-linking, and thus the glass transition temperature is lower than room temperature. The material is particularly effective in enhancing the presence of a jump region; in addition, since the size of the nanoparticles is in the same order of magnitude as the wavelength of the light, the light can be passed around without scattering and thus does not affect its transparency. The nano-powder filler is used in a small amount, does not affect the processability, and not only improves the strength and modulus, but also improves the impact strength. The nano-filler also contributes to the hydrolysis and enzymatic hydrolysis rate of the biodegradable polymer after use. The above modification methods of the nano material include a composite method (in-situ composite method and intercalation composite method), a polymerization method, and a direct dispersion method. 2) expansion Chain. The use of a highly reactive isocyanate, a difunctional epoxy, a bisoxazoline, a dibasic acid anhydride or a dialdehyde, etc., increases the molecular weight of the polymer, thereby achieving the purpose of improving the strength.

Example 1 : Making biodegradable grating sheets

1) drying the polylactic acid at 5CTC;

2) The dried polylactic acid is plasticized into a melt by an extruder at 120-190 ° C, and the melt is extruded from the die into the two rolls, and the surface of one of the rolls is machined to have the same surface curvature uniformly. The lens shape is arrayed, and the other roller is a smooth surface. The melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface.

Example 2: Making biodegradable grating sheets

1) The polylactic acid is chain-extruded in a twin-screw extruder with an isocyanate, granulated, and dried at 60 Torr;

2) The dried chain-extended polylactic acid is plasticized into a melt by an extruder at 120-190 ° C, and the melt is extruded from the die and then entered between the two rolls, wherein the surface of one of the rolls is uniformly distributed. The surface curvature lens shape array, the other roller is a smooth surface, the melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface. .

Example 3: Fabrication of biodegradable grating sheets

1) mixing polylactic acid with silica having a size of lOnm, extruding and granulating through a twin-screw extruder, and drying at 60 ° C;

2) The dried polylactic acid is plasticized into a melt by an extruder at 120-190 ° C, and the melt is extruded from the die into the two rolls, and the surface of one of the rolls is uniformly distributed. The surface curvature lens shape array, the other roller is a smooth surface, the melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface. .

Example 4: Fabrication of biodegradable grating sheets

1) drying the PHB at 70 ° C;

2) The dried PHB is plasticized into a melt by an extruder at 150-180 ° C, and the melt is extruded from the die into between the two rolls, and the surface of one of the rolls is machined to have the same surface curvature lens uniformly distributed. The shape array, the other roller is a smooth surface, the melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface. Example 5: Fabrication of biodegradable grating sheets

1) mixing PHB with 50 nm calcium hydroxyphosphate, extruding and granulating in a twin-screw extruder, and drying the pellet at 70 ° C;

2) The dried PHB is plasticized into a melt by an extruder at 150-180 Torr, and the melt is extruded from the die into between the two rolls, and the surface of one of the rolls is machined to have a uniform array of the same surface curvature lens shape. The other roller is a smooth surface, and the melt is extruded through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface.

Example 6: Making biodegradable grating sheets

1) drying the polyester amide at 80 ° C;

2) The dried polyester amide is plasticized into a melt by an extruder at 190-230 Torr, and the melt is extruded from the die into between the two rolls, and the surface of one of the rolls is machined to have the same surface curvature lens uniformly distributed. The shape array, the other roller is a smooth surface, the melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface.

Example 7: Making biodegradable grating sheets

1) After intercalating the polyester amide with montmorillonite, granulating after extrusion in a twin-screw extruder, the pellets are dried at 80 ° C;

2) The dried polyester amide is plasticized into a melt by an extruder at 190-23 CTC, and the melt is extruded from the die into between two rolls, and the surface of one of the rolls is machined to have the same surface curvature lens uniformly distributed. The shape array, the other roller is a smooth surface, the melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface.

Example 8: Making biodegradable grating sheets

1) drying the polyglycolic acid at 90 ° C;

2) The dried polyglycolic acid is plasticized into a melt by an extruder at 230-25 CTC, and the melt is extruded from the die into between the two rolls, and the surface of one of the rolls is machined to have uniform surface curvature lenses of uniformity. The shape array, the other roller is a smooth surface, the melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface.

Example 9: Fabrication of biodegradable grating sheets 1) mixing polyglycolic acid with a difunctional epoxy compound, and after extrusion granulation in a twin-screw extruder, the pellets are dried at 50 ° C;

2) The dried pellets are plasticized into a melt by an extruder at 220-250 ° C, and the melt is extruded from the die and then entered between the two rolls, wherein the surface of one of the rolls is machined to have the same surface curvature uniformly. The lens shape is arrayed, and the other roller is a smooth surface. The melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface.

Example 10: Fabrication of biodegradable grating sheets

1) mixing polyglycolic acid with dioxazoline, and extruding and granulating in a twin-screw extruder, the pellet is dried at 80 ° C;

2) The dried pellets are plasticized into a melt by an extruder at 120-15 CTC, and the melt is extruded from the die into between the two rollers, and the surface of one of the rollers is machined to have the same surface curvature lens shape uniformly distributed. The array, the other roller is a smooth surface, the melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface.

Example 11: Making biodegradable grating sheets

1) mixing polyglycolic acid with a dibasic acid anhydride, and after extruding and granulating in a twin-screw extruder, the pellets are dried at 12 CTC;

2) The dried pellets are plasticized into a melt by an extruder at 150-200 ° C, and the melt is extruded from the die into the two rolls, and the surface of one of the rolls is machined to have the same surface curvature uniformly. The lens shape is arrayed, and the other roller is a smooth surface. The melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface.

Example 12: Making biodegradable grating sheets

1) mixing polyglycolic acid with dialdehyde, after extrusion granulation in a twin-screw extruder, the pellets are

Dry at 120 ° C;

2) The dried pellets are plasticized into a melt by an extruder at 200-230 ° C, and the melt is extruded from the die into the two rolls, and the surface of one of the rolls is machined to have the same surface curvature uniformly. The lens shape is arrayed, and the other roller is a smooth surface. The melt is pressed through the two rollers, and then cooled and shaped, and a lens array having the same curvature and a biodegradable grating sheet having a smooth surface on the front surface are formed on the front surface. Example 13: Making biodegradable articles with stereoscopic images

1) using the biodegradable grating sheet of Example 1, printing a pattern on the back plane of the grating sheet to form a biodegradable lenticular sheet with a stereoscopic image;

2) After punching, place it in the front cavity of the injection molding machine, and position the sheet on the surface of the cavity with static electricity, vacuum or the tension of the sheet itself;

3) Close the mold, inject the molten plastic aliphatic polyester amide or polylactic acid into the mold, cool and harden the mold, and then open the mold to take out the product.

Example 14: Making biodegradable articles with stereoscopic images

1) using the biodegradable grating sheet of Example 2, printing a pattern on the back plane of the grating sheet to form a biodegradable lenticular sheet with a stereoscopic image;

2) After punching, put it into the mold of the extrusion blower, and adsorb it on the surface of the cavity by static electricity or vacuum or static electricity;

3) After the length of the plastic preform extruded by the extruder reaches the requirement, the mold is closed and filled with compressed gas to form;

4) After cooling and hardening, open the mold and take out the product.

Example 15: Production of biodegradable articles with stereoscopic images

1) using the biodegradable grating sheet of Example 3, printing a pattern on the back plane of the grating sheet to form a biodegradable lenticular sheet with a stereoscopic image;

2) Combining a layer of biodegradable plastic with a press or roller;

3) After the blanking, the product is made.

Example 16: Making biodegradable articles with stereoscopic images

1) using the biodegradable lenticular sheet of Example 4, printing a pattern on the back plane of the lenticular sheet to form a biodegradable lenticular sheet with a stereoscopic image;

2) coating the pattern with a biodegradable protective gel polylactic acid;

3) compound with paper, cotton or silk;

4) After the blanking, the product is made.

The product can be used in postcards, desk calendars, wall calendars, decorations and toys.

Example 17: Production of biodegradable articles with stereoscopic images

1) Printing patterns on paper, cotton or silk,

2) coating the pattern with a biodegradable protective gel polylactic acid;

3) compounding with the biodegradable grating sheet prepared in Example 5 to form a biodegradable a lenticular sheet with a stereo image;

4) After the blanking, the product is made.

The product can be used in postcards, desk calendars, wall calendars, decorations, toys and sun hats. Example 18: Making biodegradable articles with stereoscopic images

1) using the biodegradable lenticular sheet of Example 6, printing a pattern on the back plane of the lenticular sheet to form a biodegradable lenticular sheet with a stereoscopic image;

2) placing an information carrier (IC chip) on the lenticular sheet and covering the biodegradable plastic substrate;

3) After punching, put it into the hot press mold and heat it up, take it out, and cool it to get the product.

The product can be used for a bank credit card with an information carrier, an identification card, a product identification card, an item origin tracking card, an animal such as a pig immunization card, and the like.

Example 19: Making biodegradable articles with stereoscopic images

1) using the biodegradable grating sheet of Example 7, printing a pattern on the back plane of the grating sheet to form a biodegradable lenticular sheet with a stereoscopic image;

2) coating the pattern with a biodegradable hot melt adhesive aliphatic polyester after punching;

3) placing a wooden board on the lenticular sheet;

4) Put it into the mold of the hot press, close the heat press and take it out, and then cool it to get the product. The product can be used for furniture decoration materials and advertising materials, such as short-time furniture, disposable appliances, billboards, posters, sun hats and road signs used in large sports games, fairs, or exhibitions.

Example 20: Making biodegradable articles with stereoscopic images

1) using two biodegradable lenticular sheets of Example 8, printing a pattern on the back plane of the two lenticular sheets to form a biodegradable lenticular sheet with a stereoscopic image;

2) After punching, place a lenticular sheet face down on the hot press template, and place a layer of opaque material such as wood, paper, etc. on it, and place it on top with biodegradable hot melt. a lenticular sheet of glue, the lenticular sheet facing upward;

4) The closed hot press is taken out after heat sealing, and after cooling, a double-sided raster image with a stereo image is obtained. The article can be used for articles requiring double-sided decorative effects such as screens, billboards, road signs, and the like.

Claims

Claim

A biodegradable grating sheet characterized in that: the grating sheet is made of a biodegradable polymer or a modified product thereof.

2. The biodegradable grating sheet of claim 1 wherein: said biodegradable polymer is a synthetic biodegradable polymer or a naturally biodegradable polymer.

3. The biodegradable grating sheet according to claim 1, wherein: the modified material is a composite method, a polymerization method or a direct method using nano silica, nano montmorillonite or nano calcium calcium phosphate. Biodegradable nanocomposites formed by dispersion modification.

4. The biodegradable grating sheet according to claim 1, wherein: the modified product is a highly reactive isocyanate, a difunctional epoxy, a dioxazoline, a dibasic anhydride or a dialdehyde. A biodegradable polymer formed by chain extension.

5. A method of making the biodegradable lenticular sheet of claim 1 comprising the steps of:

1) drying the biodegradable polymer or its modification at 50-12 CTC;

2) Extrusion into a sheet by an extruder at 120 to 250 ° C, the front side of the sheet having a uniform lens array of the same surface curvature, which is cooled and shaped to become a biodegradable grating sheet.

6. A biodegradable stereographic image article made from the biodegradable grating sheet of claim 1 wherein: said grating sheet is a biodegradable polymer or a modified product thereof. production.

7. The biodegradable stereographic article of claim 6 wherein: said biodegradable polymer is a synthetic biodegradable polymer or a naturally biodegradable polymer.

The biodegradable stereoscopic image-bearing article according to claim 6, wherein: the modified material is a composite method using a nano-silica, a nano-montmorillonite or a nano-hydroxy calcium phosphate, and a polymerization method. Or a biodegradable nanocomposite formed by direct dispersion modification.

9. The biodegradable stereographic article of claim 6 wherein: the modification is a highly reactive isocyanate, a difunctional epoxy, a dioxazoline, a dibasic anhydride or A biodegradable polymer formed by dialdehyde chain extension.

10. A method of producing a biodegradable stereographic article according to claim 6 comprising the steps of:

1) forming a biodegradable grating sheet into a lenticular sheet with a stereoscopic image; 2) Make products with stereoscopic images.

11. A method of making a biodegradable stereographic article according to claim 10, wherein: step 1 is to print the pattern on the back plane of the biodegradable lenticular sheet.

12. The method of manufacturing a biodegradable stereographic article according to claim 10, wherein the step 1 is to print or print the pattern on the back plane of the biodegradable grating sheet. Biodegradable protective or hot melt adhesive.

13. The method of manufacturing a biodegradable stereographic article according to claim 10, wherein the step 1 is to print the pattern on the back plane of the biodegradable grating sheet, and biodegradable. Substrate compounding.

14. The method of manufacturing a biodegradable stereographic article according to claim 10, wherein the step 1 is to print the pattern on the back surface of the biodegradable grating sheet on the grating sheet. The information carrier is placed and then combined with a biodegradable substrate.

15. The method of manufacturing a biodegradable stereographic article according to claim 10, wherein the step 1 is to print or print the pattern on the back plane of the biodegradable grating sheet. A biodegradable protective or hot melt adhesive is compounded with a biodegradable substrate.

16. The method of producing a biodegradable stereographic article according to claim 10, wherein: step 1 is to composite the biodegradable lenticular sheet after printing the pattern on the biodegradable substrate.

17. The method of manufacturing a biodegradable stereographic article according to claim 10, wherein: step 1 is: after printing the pattern on the biodegradable substrate, placing the information carrier on the substrate Biodegradable lenticular sheet composite.

18. The method of manufacturing a biodegradable stereographic article according to claim 10, wherein: step 1 is to print or print biodegradable protection after printing a pattern on the biodegradable substrate. The glue or hot melt adhesive is combined with the biodegradable grating sheet.

The method for producing a biodegradable stereographic article according to claim 12, 15 or 18, wherein: the protective adhesive is an aliphatic polyester or an aliphatic polyester amide, and the hot melt adhesive It is an aliphatic polyester, an aliphatic copolyamide or an aliphatic polyester amide.

20. The method of producing a biodegradable stereographic article according to claim 13, 14, 15, 16, 17, or 18, wherein: said biodegradable substrate is paper, leather, cotton, Silk, biodegradable nonwovens, biodegradable plastic or wood.

21. A method of fabricating a biodegradable stereographic article according to claim 10, The method is characterized in that: step 2 is to make a product with a stereoscopic image after punching.

The method for manufacturing a biodegradable stereoscopic image product according to claim 10, wherein: step 2 is to make a stereoscopic image after blanking and then engraving the pattern or text.

P

23. The method of manufacturing a biodegradable stereographic article according to claim 10, wherein: step 2 is punched and then placed in a mold, using an injection molding machine, an extrusion blow molding machine, a molding press, and a hot press. The machine or the laminator is molded, and after cooling and hardening, the article with the stereo image is taken out from the mold.