TW440575B - Injection-molded product of polyglycolic acid and production process thereof - Google Patents

Abstract

The invention provides an injection-molded product of polyglycolic acid obtainable by molding a thermoplastic resin material at an injection temperature ranging from the melting point, Tm of the polymer to 255 DEG C, wherein the thermoplastic resin material comprises polyglycolic acid having a repeating unit represented by the following formula (1), and the following physical properties: (a) the melt viscosity, η* [as measured at a temperature of (the melting point, Tm of the polymer + 20 DEG C) and a shear rate of 1,000/sec] being 30-10,000 Pa.s; (b) the melting point, Tm being at least 150 DEG C; (c) the melt enthalpy, ΔHm being at least 20 J/g; and (d) the denisty being at least 1.50 g/cm<SP>3</SP> as measured in an unoriented, crystallized form, and a production process thereof.

Description

V. Description of the invention (1) 1 Fan Ming's hot acid alcohol is polymerized and contains two types of substances that can be ejected from the material type II. 1 In relation to Mingfa's strong method, restrain its impact and rush 'resistance, type into solution burst Medium acid soil alcohol refers to the excellent shape and uniformity of the material, such as ethoxylate, etc. The material is hot fat, tree, flexible, flexible, and fast-food. Soaked in water, such as in water, it is opened with a container. Cook with a pattern of 8 inches of body acid, alcohol-based poly-polymer Ming Dianfa, Ben Wenfan Fan Guangguang and other types of disposable meals, utensils Xironglangpin sent to the hair plastic The amount of K, but the question of the big question will be uncomfortable, so the big security will be a heavy period ο for a long solution, and the ability to increase energy can be easily increased. The high school abandoned the waste for the environment. Plastic Da Zi, the material is coming from the material, the annual output is nearly high. ¾ Questions about the copolymerization of allenes such as alkenes, etc., and the polymerization of ethylenene into ethylene, including the rational management of the waste, such as the disposal of plastics, such as the rejection of gums, etc. S Long AB Ni, 'Ethylene Ethylene Benzene Polyvinyl Acetate.' Polyester and other resins Chlorobutene and other acids such as methacrylic acid diethylene terephthalate, Polyester, Resin based resin amine type into injection molding. Fat All kinds of esters, carbonic acid, polyr, aldehydic polycondensation in tree species I -------- L 1 pack-(谙 Please read the precautions on the back before filling this page),-= 5 Central Bureau of the Ministry of Material Economy Employee consumer cooperatives print molecular solutions that break down and disintegrate soils in high schools. T-negative M. In the habitat that disintegrates and disintegrates, the soil in the microcyclic soil is clear to the eyes. The f-set is the solution, and the meristem species have a higher meristem. In the case of sexual materials and materials, the impact is not yet complete, so we must wait for the physical properties of the economy to be produced, the plastic rubber and the plastics, and the fusion of the melt, the heat can be resistant, the evaluation KI3J strengthened} 'Sexuality The sexual solution of the injection-molded plastic is clearly displayed and requires b full marks. Ο The paper size is applicable in the country. _ Country 彳 (rN, w… Luo 丨 2 ΐ () &gt; α (π 公 漦)

V. Description of the invention (2) In conventional biodegradable plastic injection moldings, such as injection molding with M starch as the matrix, it cannot meet the requirements of strong toughness and heat resistance, and it is difficult to make injection molding due to non-crystallinity. The problem. The injection moldings based on M cellulose androgen are unsatisfactory in terms of impact resistance, toughness, and heat resistance, and are difficult to injection molding because of low crystallinity. The production of injection moldings based on polyester produced by MICROBIOLOGY has a very large cost problem. Injection moldings based on synthetic polyesters such as Μ polysuccinate, except for impact resistance, toughness, and heat resistance, which are not satisfactory | There are also succinic acids or butyl materials that are not satisfactory for injection molding Diols are quite expensive. An injection molded product using a semi-synthetic poly-lactic acid as a matrix requires high purity of optically active L-lactic acid used as a raw material, which must be manufactured by a K-fermentation method, and the low cost is an essential factor. In addition, since polylactic acid has a high glass transition temperature Tg, it is difficult to compound polylactic acid under normal compounding conditions. SUMMARY OF THE INVENTION The object of the present invention is to provide an inexpensive plastic injection molded product which has excellent impact resistance, toughness, heat resistance, etc., and exhibits disintegrability in soil. The present inventors made diligent research results in order to overcome the problems of the aforementioned conventional technology, and found that the injection molding formed of a thermoplastic resin material containing polyglycolic acid having specific physical properties has soil decomposability, and at the same time, impact resistance, toughness, It has excellent heat resistance, etc., and possesses physical properties that can sufficiently replace conventional plastic injection moldings that have become a problem in plastic waste, and can be manufactured at a lower price. --4- This paper is compliant with the China National Standards (CNS) of the State of China (8), 4 (2 丨 (&乂; 297 公 #_) ------! ---! ---- I Good-- ----- Ding ----- Quan (谙 Please read the notes on the back before filling this page) Printed by the staff of the Central Bureau of Standards of the Ministry of Economy

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, heated in the presence of catalysts (such as cationic catalysts such as tin carboxylates, tin halides, and antimony halides), obtained by block ring-opening polymerization or solution ring-opening polymerization . In order to obtain polyglycolic acid having excellent physical properties, it is preferable to use high-purity glycolide as a monomer. The high productivity of high-purity glycolide is produced by mixing glycolic acid oligomer with a high boiling point polar organic solvent, and heating under normal pressure or reduced pressure to a temperature that causes the oligomer to depolymerize. The polymer is depolymerized in a state of being formed into a solution phase, and the produced glycolide is distilled off with a high-boiling polar organic solvent, and glycolide is recovered from the distillate. A method for producing an injection molded article from polyglycolic acid includes, for example, a method of granulating polyglycolic acid alone or a composition containing polyglycolic acid, and then supplying the pellet to an injection molding machine and injection molding. Polyglycolic acid can use C 0, Η 20, and C Η 20, or extremely cheap raw materials such as ethylene glycol, and can be mass-produced industrially. Polyglycolic acid injection molded products are disintegrating in the soil and are environmentally friendly. The load is small. The present invention has been completed based on this knowledge. According to the present invention, there is provided a polyglycolic acid injection molded product, which will have a repeating unit represented by the following formula (1): (a) melt viscosity r? # [At temperature (melting point T m + 2 0 tn, shear speed 1 , 0 0 0 / sec measured] 3 0 ~ 1 0, 0 0 0 P as, (b) melting point Tm at 150CM, (c) melt heat content Λ Η π at 20 J / g Μ, Ｍ 和 -5-(Please read the precautions on the back before filling this page) 丨 Loading,-° The thick scale of this paper is applicable to the standard of the Chinese cabinet (CNS) Λ4 ,: _ι i 4Φ〇 ^ _Γ / ¾Indicate that A7 B7 (bucket (d)) non-oriented crystals with a density of 1.5 Q g / c nt or more of the polyglycolic acid thermoplastic resin material, at the injection temperature T m ~ 2 5 5 ° C temperature range According to the present invention, there is also provided a method for producing a polyglycolic acid injection molded article, which comprises: having a repeating unit represented by the following formula:

0 — CH2 — C -II 0 (a) Melt viscosity 77 ”[Measured at temperature (melting point T m + 2 [TC), 1, 0 0 0 / second :) 3 0 to 1 0, 0 0 0 P a · s, (b) the melting point T m is above 15 ϋ ° C, (c) the melt heat content △ H in is above 20 J / g, and (d) the density of non-oriented crystals is in] .50 g / C η 3 or more Polyglycolic acid thermoplastic resin material pellets, injection molding metal mold for injection molding machine, cylinder 25 ° C, metal mold temperature (Γ ~ T m, injection pressure 1-out molding, and if necessary, at the crystallization temperature Tc i ~ Tm. Minutes to 10 hours. In the injection molding of the present invention, Izod impact strength (no pure resin of more than 20 km 2 of polyglycolic acid) (Neat out of molded articles, especially polyolefins with high impact resistance, polybutylene terephthalate, polyacetal, polycarbonate, etc. The present invention is injection molded into plastics, with a flexural strength of 1. Π Ο Μ P The injection of pure resin of polyglycolic acid with the number of properties in P a and h can be used as a high-rigidity problem in plastic waste. -fi a paper) Eight 4 specifications (difficult) Shearing speed is supplied to the installation temperature T m ~ '1 (1 4 H Pali temperature annealing) notch, 25 °. Resi η), ABS resin and other substitutes. Molded Product Molded Product Substitute the Consumers 'Cooperation of the Central Standards Bureau of the Ministry of Economic Affairs to print the printed I' ^ ·. ~ Packing -------- Order j ------- line (please read the precautions on the back before filling in this (Page) 〇 ~ 5 7 V. ¥ Description A7 B7 (5) (1) Substitute. Injection molding of the present invention, injection molding of pure resin of polyglycolic acid on tensile strength of 60MPaM and elongation of 5SJK It can be used as a substitute for the high-intensity injection molding that is a problem in plastic waste. 馘 Detailed description of the polymer structure The polyglycolic acid used in the present invention is a polymer having a repeating unit shown in the following formula: 〇- ch2-c-

The proportion of the repeating unit represented by formula (II) in the II 0 polymer is usually more than 70 weight Si, more preferably K80 weight $ M, and more preferably M80 weight% M. When the proportion of the repeating unit represented by the formula (1) is 70% by weight or less, the original crystallinity of the polyglycolic acid is exhibited, and the impact resistance, toughness, and heat resistance of the injection-molded article are reduced. The repeating unit of the repeating unit M 舛 shown in formula (2) is, for example, the repeating unit shown in formula (1):

O-fCHAO—C + CH 丄 C-.11 II 0 〇⑵ --- ^ ---- .. 1 pack 丨 ----- order ------ line (Please read the precautions on the back first (Fill in this page again) Printed by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (where 10, m = 0 ~ 10)

Ο-CH I where j = 1

C II The repeating unit shown in the following formula (3) • (3) (CHAH 〇10), the repeating unit shown in the following formula: (Paper team standard Tong / f) National Standard (CNS) Λ4 圯 grid (2 丨 (} /: 297 mm)

Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economics (where R i and R 2 are each independently a hydrogen atom or a C i to C 10 alkyl group) &gt; M and the repeating unit shown by the following formula (5): + 〇- CH2 —0 —CH2 —CH2 + (5) These repeating units (2) to (5) are 1 weight; (; when the above ratio is introduced, because the melting point Tm of the polyglycolic acid homopolymer decreases, the processing temperature of the polymer It can reduce the thermal decomposition during melt processing. In addition, by controlling the crystallization rate of polyglycolic acid by copolymerization, the injection moldability can be improved. On the other hand, when these repeated units are more than 30% by weight, (5), Polyglycolic acid is inherently impaired in crystallinity. Polymer objects <Molecular weight-Melt viscosity> The polyglycolic acid of the injection molding material of the present invention is a high molecular weight polymer. The melt viscosity can be an indicator of molecular weight. Used in the present invention Polyglycolic acid, melt viscosity η * measured at temperature (T m + 2 0 t :) (ie equivalent to normal melt processing temperature) and shear rate 1, 0 0 0 / second is 3 0 to 1 0 , 0 0 0 Pa_ s, preferably from 50 to 8, OOOPa. S, MM100 to 5, OOOPa.s is even better. Melting of polyglycolic acid When the body viscosity η κ is less than 3 0 P a · s, the mechanical properties of the obtained injection molded product are insufficient. On the other hand, when the melt viscosity η # of the polyglycolic acid exceeds 1 0, 0 0 0 P a · s, the injection is performed. Insufficient fluidity during molding, there may be a shortage of filling of the Jinlong horizontal cavity. —8 1 (Please read the precautions on the back before filling the nest page). —Installation,-&amp; .mU . 4 '1, Standard of the Illustrator (CNS) Λ4 specification (210 X 297 foot)

Α7 Β7 V. Description of the invention (7 &lt; Thermal performance &gt; The melting point T m of the polyglycolic acid used in the present invention is 15 (TC or more, preferably 190 ° C or more), and more than 21 ITC. The melt heat content AH m of the polyglycolic acid used in the present invention is 2 [] J / g or more, preferably 3 (U / g or more, and more than 40 J / g. T m is 1 5 (TC Polyglycolic acid below and / or ΔH in below 2 DJ / g has a crystallinity reduction due to disordered chemical structure in the molecule, etc. As a result, it can be inferred that Tm and / or ΔHm are too low. Therefore, it is used These polyglycolic acid forms • · · ·. The formed injection molding may have insufficient impact resistance, toughness, and heat resistance. <Density> The density of the polyglycolic acid used in the present invention is 1 without orientation crystals 5 0 g / c π 3 or more, preferably 1.5 1 g / cm 3 or more, and more preferably 1.5 2 g / cm 3 or more. This density is 1.5 () g / cm 3. The following polyglycolic acid has a disordered intramolecular chemical structure and causes a decrease in crystallinity. As a result, it is estimated that the density T. decreases. Therefore, using such a low-density polyglycolic acid injection molded product, That is, there may be insufficient crystals, insufficient impact resistance, strong tenacity, heat resistance and so on. "Printed by the Sheller Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) ... [Disintegrability in soil] of the _virtual_crack .. &amp; ... The injection molding of the present invention is a disintegrable molding in soil with less environmental impact. 的 Injection of the polyglycolic acid of the present invention When it is buried in the soil at a depth of 10 c ni, it usually disintegrates within 24 months, preferably within 12 months, and loses its original shape. For example, in the case of conventional injection of polylactic acid into plastic, -9-This paper size applies to the Chinese national standard {cns) Λ4 specification U] ox2y〃Public radius) Printed by Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () The vitrification temperature is too high. Under normal conditions, there are The problem of difficulty in compounding. In contrast, the injection molded product of the present invention is formed of polyglycolic acid with a lower T g. 1 It can be compounded under normal conditions. Izod impact strength (no notch, 2 5 ° C) high, with an extremely high impact strength of 20 k J / m 2 or more, preferably 3 [K k / m 2 or more, more preferably 4 G k J / ra 2 or more. Injection moldings with these high levels of Izod impact strength are rare in injection moldings that disintegrate pure resins that have never contained a thorium impact modifier. These highly impact-resistant polyglycolic acids are used as pure resins, or in combination with impact modifiers, etc., to obtain injection-molded articles which are more resistant to disintegration in the soil. It is not a pure resin of polyglycolic acid, but a composition made by blending various ballasts or thermoplastic resins here, or a composition obtained by mixing an impact resistance modifier here, can obtain a soil with extremely strong impact resistance. Medium disintegrating injection molding. When the Izod impact strength of the injection molded product is low, soil damage may occur during transportation or use. Injection moldings for tough parts Use specific polyglycolic acid before use to obtain injection moldings that are highly resistant to buckling stress. More specifically, according to the present invention, it is possible to obtain an injection molded article having a buckling strength of generally 1 [) fi Μ P a or more, preferably [50 Μ P a or more, and more preferably 2 〇 Μ P a or more . Regarding the buckling elastic pseudo number, it is possible to obtain an injection-molded product usually having a G G a of 5 or more, preferably a G G a or more, and even more a 7 G G a or more. In terms of pure resin, it has such a high degree of buckling strength or buckling-1 0-this paper size is suitable for leisure time W ('NS) ΛΟϋ 格 (210X21 dead male f_)-^ ---- Κ--ji 装 丨- --- Order ------_ Line (Please read the notes on the back before filling this page)

Disintegrative injection moldings of elastic pseudo-numbers in the soil are produced by printed materials of the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, and are conventional resin-disinjectable moldings. Polyglycolic acid as a pure resin, or a composition obtained by using this as a matrix resin, can provide disintegrative ejection into concrete with extremely rigid and viscous soil never seen before. According to the present invention, it is possible to obtain an injection molded article which is strong against tensile stress. More specifically, according to the present invention, it is possible to obtain an injection-molded product having a size of 6 G G P a or more, and fMi M P a or more is preferable, and t G Q M P a or more is more preferable. It is based on that the tensile elongation rate is usually more than 5%, preferably more than 7%, and more than 9%-*,. Good. Injection moldings exhibiting such high tensile strength or tensile elongation are rare in conventional biodegradable plastic injection moldings. When polyglycolic acid is used as a pure resin, or a composition made from this resin, it can provide disintegrating injection moldings in soil with unprecedented strength and viscosity. Injection molding m. Manufacturing method, &lt; raw polymer &gt; The polyglycolic acid of the raw material for the injection molding of the present invention can be prepared according to the following methods ① and ②. ① Polyglycolic acid can be glycolide from glycolic acid dimer ester. In the presence of a small amount of catalyst (such as cationic catalysts such as organic acid, tin halides, tin halides, antimony halides, etc.), it is heated to about 2 to 2 5 0 UC temperature, prepared by ring-opening polymerization. The ring-opening polymerization is preferably a block polymerization method or a solution polymerization method. ② Polyglycolic acid can be obtained by polycondensation of glycolic acid or alkyl glycolate, heating in the presence or absence of catalyst, dehydration and dealcoholization. To obtain a polyglycolic acid copolymer, in the above method ① or ②, the paper size of the copolymerized paper is subject to the Chinese National Standard (CNS) Λ4 and (2 丨 0〆2) 7mm 炤) I '^-;. ~ Install ------ order ------- 1 line (please read the precautions on the back before filling this page)

A7 B7 pentamidine ο oxane θ ′ V ester, 41¾-X _ propane (cold ene such as ethyl acetic acid 草 grasses such as esters, there are esters of monoesters 0 esters of pentamide 'esters of 7 methyl A I θ * 'Purpose § Valeryl δ r Purity s. Propyl Valprolactone Milk Hexyl Group Lipid Hydroxyl Mono 6-Alcohol, Butyl Bicyclo Acid Butane 4 Alkyl 1, Purity Hydroxy, Di 4- Alcohols 3, 2, 1, ethyl ethane and butyl; 3, esters, esters, hydroxy acids, 3 carbons, their formic acid or propionic acid, triyl carboxyl, hydroxy, 3-hydroxy, etc., and other acid esters ethyl and alkanes, which Above. With M, or species, carboxylic acids and other carboxylic acids, these two are equivalent to the family can be lipids; acid compounds in combination. Mixed, reacid erodibutin and the above, the quality of alcohol and the two together should be polymerized. The anti-shared group M has vinegar and is selected by itself. When the alcohol is added, the alcohol is suitable for the purpose. The alkyl group can synthesize the acid and also the alcohol. The other acid is the acid. Alcohol monoalcohol, ethyl ether, polyethylene terephthalate, S ester, and so on. (2) --------- ir equipment-(谙 Please read the notes on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Printed by Bayer Consumer Cooperative It can be obtained by reaction. Among the above-mentioned production methods, the ring-opening polymerization method of glycolide of M① is preferable, and high molecular weight polyglycolic acid is easily obtained. In the method of ①, the glycolide used as monomer is a conventional glycolic acid oligomer It is obtained by the sublimation depolymerization method, and the solution phase depolymerization method (Japanese Patent Application No. 8-48000) developed by the present inventors has high purity, high yield, and can be obtained in large quantities, so it is preferred. Monomer When using high-purity ethylene glycol, it is easy to obtain high molecular weight polyglycolic acid. The solution phase depolymerization method is to dissolve the glycolic acid oligomer with at least one high boiling point polarity with a boiling point in the range of 2 3 0 ~ 4 50 ° C. A mixture of organic solvents is heated at a temperature at which the oligomer depolymerizes under normal pressure or reduced pressure, and the oligomer is dissolved in the solvent, so that the residual liquid phase ratio (volume of the oligomer) Ratio) to 0.5 M, (3) continue to further heat at this temperature, depolymerize the oligomer, and then dimerize the resulting dimer cyclic ester (ie, ethylene-1 2-this paper is suitable for China according to scale) National standard 隼 (CNS):… · -N7 public potential V. Explanation of ¥ (11 A7 B7 lactide) and high boiling point polar organic The solvent is co-distilled, and (5) glycolide is recovered from the distillate. High-boiling-point polar organic solvents include bis (alkoxyalkyl esters) such as di (2-methoxyethyl) phthalic acid, and the like. ), Alkanediol dibenzoates such as diethylene glycol dibenzate, aromatic carboxylic acid esters such as benzyl butyl dibenzoate, or dibutyl phthalate, tricresyl Aromatic phosphoric acid such as phosphoric acid ester and the like are usually used in the ratio of 0.3 to 50 times the amount (weight ratio) of this oligomer. If necessary &gt; Use this oligomer together with a high boiling point polar organic solvent • · .. * Solubilizers such as polypropylene glycol, polyethylene glycol, tetraethylene glycol, etc. The depolymerization temperature of glycolic acid oligomers is usually On 2 3 0 ° C ants, preferably 2 3 0 ~ 3 2 Ο υ. The depolymerization is carried out under normal pressure or reduced pressure, and the depolymerization is preferably carried out by heating under reduced pressure from 0.1 to 90.0 kPa (1 to 900 mbar). The material is resinous, plastic, and thermally pure. It is used for the polymerization of pure acrylic acid and ethylene. The material can be used as the resin, plastic, and heat. Make the things can be made, and the group of agents within the group can be shaped, and the nature of the fat tree can hinder the plastic, so it can be hot, and the fat filling machine is mixed with the tree. ο Its 0 tf 1 part acid weight alcohol weight ethyl 00 poly 7 Yui Wei, filling material can be used for photo materials, no weight S weight: ----- ^ --- ^! -pack ---- --Order ------ line (谙 first read the precautions on the back and then fill out this page) ο the Central Consumers Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives in the printing of hot prints are not adequate or reheated ο resistant I ο Fill 2, the machine is not super tough. Agent strength} plastic, material can be mixed or strong (, hitting the material, ¾ the amount of weight and resistance to the weight of the group ο 10 kinds of agents, such as plastic over plastic resin beyond the quantitative properties of the fat injection remodeling, oxocalcium fb acid, oxygen, aluminum calcium calcium silicic acid, calcium calcium silicic acid, carbonized oxygen, boron low aluminization to reduce oxygenated oxygen, iron feed ib molten oxygen filling machine, and no titanium, The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

V. Hair! ^ Ming (丄 2) 1 calcium acid, magnesium carbonate% magnesium silicate magnesium phosphate kaolin, slip 1 powder mica, magnetic iron, carbon silicon, silicon nitride molybdenum disulfide V glass 1 1 total titanic acid And other powder whisker fibers, etc. This can be used separately or in combination with each other. First, it can be used in combination with one kind of K. Relative to 100 parts by weight of polyglycolic acid * Inorganic filler η 1 Materials are usually available in 0-1 00 parts by weight &gt; In order to take into account the impact resistance, toughness, etc., K is preferably used in the range of 0. 0 1 50 parts by weight. 0 5 10 Note 1 # 1 part by weight is better. Item 0! Other thermoplastic resins have Homopolymers and copolymers of lactic acid and ethylene oxalate are filled in. · Polymers and copolymers ε-caprolactone homopolymers and copolymers, polysuccinate Έ 1 I m polyhydroxybutyric acid, hydroxybutyric acid- Hydroxyl Acid copolymer acetic acid 1 1-dimensional vitamin polyvinyl alcohol I starch, polyglutamic acid natural rubber, polyethylene 1ene, polypropylene styrene-butadiene copolymer rubber acrylonitrile-butadiene copolymerization Rubber polymethacrylic acid methyl 0% styrene styrene stupid ethylene-butadiene styrene styrene block copolymer styrene-ethylene butene-styrene 1 1 block copolymer ABS resin Λ MBS resin., Ethylene-ethylene Alcohol copolymerization 1 I, etc. 0 These thermoplastic resins can be used separately ... or two kinds of shanghai 1 1 〇 Relative to 100 parts by weight of polyglycolic acid f Other thermoplastic resins can usually be used | 0 ~ 1 00 parts by weight t However, in order to take into account the collapse of the impact-resistant strong and tough soil 1 1 and so on, the use of K is 50 weight, the part below is better t, and the ratio of M 1 to the weight ratio of 1 1 is better! The plasticizer has di (methoxy Ethyl) phthalate, dioctyl Benzene diesters diethyl phthalate, benzyl butyl benzate, etc. Benzene 1 ί formic acid _ »Diethylene glycol-'' benzoate I Formic acid m Octyl adipate, octyl adipate, octyl sebacate and other aliphatic dibasic acids Θ purpose »Ethyl 1 1 I -1 4- 1 1 1 I This paper is in accordance with the Chinese Cabinet Standard (CNS) Λ4 size (210X M7 male) 44 0 5 7 6 A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5、1 Instructions (13) 1 1 ny * m-based tributyl citrate and other aliphatic tribasic esters (dioctyl phosphate N phosphoric acid) 1 I Phosphate esters such as xylyl esters, epoxidized soybean oil, etc. 1¾ Oxygen plasticizers 9 Poly 1 1 Polyethylene glycol sebacate, polypropylene glycol lauric acid, etc. Polyalkylene glycol esters, etc. Please 1 I These plasticizers It can be used alone or in combination on two kinds of Μ. Relative to Ju 1 1 ethanol 100 parts by weight of plasticizer can usually be used. 0-200 parts by weight. © I 1 I i In consideration of impact resistance, toughness, heat resistance, etc., kK is used at 100 weight. Note 1 I matter 1 part by weight M is better f It is better to make the ratio of 50 parts by weight or less. The present invention can be added if necessary. 1 Add a thermal stabilizer to the thermoplastic resin material and fill in this package. I Light stabilizer, moisture-proof agent, water-repellent agent, lubricant, release agent. 1 Page 1 Coupling agent Yanke dyes and other additives. Where are these various additives 7 I \ Depending on the individual use of 100% effective amount of 0 1 I The composition is generally prepared by using polyacetic acid and inorganic fillers as needed. 、 Other additives for thermoplastic resin plasticizer __. Species M &gt; Supply to the kneading extruder-At the cylinder temperature Tm 25 5 ° ct Usually 150 ~ -2 55 ° C) 1 Melt mixing t Extrusion cooling cut [Wt- break · * made into granules 0 Melt mixing temperature [When the degree exceeds 2 5 5, the polymer is liable to cause thermal decomposition, and the molecular weight is drastically lowered [there may be a risk of foaming when the t is reduced. 0, 'Water 1 &lt; Production of injection moldings> 1 I The injection molding of the present invention is produced by J. The particles composed of the 1 1 pure resin containing the polyglycolic acid and the composition containing the polyglycolic acid are supplied to the injection molding. The injection molding machine t for the metal model is at the cylinder temperature Tm 1 I 2 5 5. . ί is usually 1 0 0 ~ 2 5 5 ° C), the metal horizontal temperature is 0V Tm 1 1 (usually 0 ~ -1 9 0) 9 injection pressure 1 n -1 0 4 Ρ Ρ a (Ml 0 ~ -1 04 HPa 1 | better) injection molding &gt; if necessary &gt; at the crystallization temperature Tc 1 τπ (usually 1 I -1 5- 1 1 1 1) recognition standard Shizhou China National Standard (CNS) Λ4 specifications ( 210X 297 male iridium) 44 05 T ~ § production _ ^ __ five, / Ming description (1 bucket) 7 0 ~ 2 2 0) annealing at a temperature of 1 minute to 10 hours. The temperature of the cylinder exceeds P and Yu Zhi's bubble when it converges. The reduction caused by the reduction of all the detonators of I® is significantly different from the thermal decomposition of the physical machine. The shape of the mechanical machine can be ejected, such as ββ, which is relatively high and high. Product, general purpose. Sex room: hit-type kitchen · Okagaya, dj eight // page 0 bottle plastic, 1 &gt; type micro-box special case into, etc. Sour change: mellow, hot, melamine-resistant, poly, and lighter than the high-grade, cookable cookware meal B. Spoon 6 * hr, discard &gt; throw away. CUEc for waiting cabinets—everything is different from each other (, shots, meals, meals, food, food, food, etc., water, etc., cups, etc., bowls, etc. In addition to the excellent performance of the device, the homogeneity of the homogeneous material can be heat-resistant, fire-resistant, acidic, alcohol-resistant, and strong. Polymerization and supply are available at low prices and are resistant to M. However, the nature of the solution is divided into local soil and soil. The example was created by shooting plastics, plasticity, good questions, good things, etc. to discard this waste. The use of cooking-type cooking utensils, electrical appliances, discarded products, electrical appliances, appliances, foodstuffs, foodstuffs, body-speed devices, and so on. (Please read the precautions on the back first) (Fill in this page again) Printed by Mingfa Benming, a staff consumer cooperative of the Central Biaohua Bureau of the Ministry of Economic Affairs. Comparison of examples of bodyware and examples. Body fusion (1) polyπ fusion is made to make an appointment with the platelet ill. Crystal knot clock ο Sub-standard 5 refers to the amount of heat added 50 points ί This paper is applicable to the national standard rate (CNS) 8 4 specifications (2 丨 〇y.297 mm) ^ 4-0 ^- 7-6

CAPIROGRAPH (made by Toyo Seiki Co., Ltd.) with nozzles printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (5) Invention Description (/) as samples, i) = f). 5 mm, L = 5 mm The thermal properties of β ⑵ polymer were measured at temperature (T III + 2 G ° C) and shear rate 10 G 0 / s. Amorphous Η with a polymer thickness of about 0.2 m ri was used as a sample. Scanning calorimeter (1) SC, Me 11 1. e! Company TC-1 0 Α), heating under nitrogen flow at a rate of 0 ° C / min, measuring the crystallization temperature (T c 1), melting point (T m), and heat content of the melt (AH m). However, the glass transition temperature (T g) is measured at a temperature increase rate of 5 ° C / min. (3) The density of non-oriented crystals is about (Γ. 2 m in amorphous Η, where each polymer is thermally fixed at 5 ° C for 5 minutes, as a sample, according to JISR-7 2 2 2 (using n-butanol The specific gravity tube) is measured. ⑷ Izod impact strength (2 5 ° C, no notch.) Measured according to JISK-7 U 0 method. ⑸ Buckling strength and flexural elasticity 傺 number is measured according to JISK-7 1 13 method. ( 6) Tensile strength and elongation were measured according to the method of Ji SK-7 1 1 3. Disintegrability in vermiculite The test of the tensile properties of each polymer was buried in dry soil with a depth of about 0 on each The observation shape was dug out in half a month. When the shape began to disintegrate, the disintegrability in the soil was evaluated when the disintegration started within 2 to 4 months. Synthesis .. Example 丄 灵 ... 体 _ 合 戚 -1 7- ^ —- &gt; 1--1 —-I ti ^ — ^^^^ 1 l, n ^ i (Please read the notes on the back before filling this page)

The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is printed in a 1 ο high-pressure autoclave, filled with polyglycolic acid (Wako Pure Chemical Co., Ltd. product) 5. 25 kg, while stirring, from 170 ° C to 2 0 〇 υ is heated up for about 2 hours, the generated water is distilled off, and K is coagulated. Next, the pressure was reduced to 20 kPa (200 milliE), and the mixture was kept for 2 hours to distill off low-boiling components to prepare a glycolic acid oligomer. The melting point Tm of the oligomer was 205 ° C. Take 1.26 kg of glycolic acid oligomer and fill it into a 10 kg flask, add 5.25 kg of benzyl butylphthalic acid (a product of Pure Chemical Company) and a solubilizer polypropylene glycol (a product of Pure Chemical Company, ft 4 0 0) 158 g, in a nitrogen atmosphere, under a reduced pressure of 5 kPa (50 mbar), heated to 270 it, the solution phase of the oligomer was depolymerized, the resulting Diethylene glycol is co-distilled with benzyl butyl benzene dicarboxylic acid. The obtained co-distillate was added with about 2 times the capacity of cyclohexane, and glycolide was precipitated from benzyl butylphthalic acid. The glycolide was then recrystallized with ethyl acetate, and dried under reduced pressure to obtain glycolide. The yield is about 78¾. Polymer Preparation Example 1 210 g of glycolide obtained in Synthesis Example 1 was filled in a cylinder made of PF A, and nitrogen was blown in and dried at room temperature for about 30 minutes. Next, add Sn C 1 4 · 6. 5 Η 2 0 0. 0 4 2 g as a catalyst, blow in nitrogen, and maintain 170 TO polymerization for 2 hours. After the polymerization is completed, cool the cylinder to room temperature. The block polymer taken out from the cylinder was pulverized to fine particles at about 3 mm, and dried under reduced pressure at about 150 and about 0.1 kPa overnight, and the remaining monomers were removed to obtain polyglycolic acid (polymerization物 P-1). Repeat the same method to prepare the necessary amount of polymer (P-. Polymer Preparation Example 2) Polymerization Example 1 was performed with the same polymerization and post-treatment, but glycolide-1 8-this paper standard is common Chinese national standard (CNS) Λ4 specification (2j〇X 297 mm)---i----In-^ .1---»nn---eJI-------(Please read the precautions on the back first (Fill in this page)

V. Description of the invention (17) (Please read the precautions on the reverse side before filling out this page) 210 g of glycolide 200 g and ethylene oxalate (1,4-dioxane-2,3-dioxine) 10 G of the mixture to obtain a glycolic acid-ethylene oxalate copolymer (polymer P-2). The same method was repeated to prepare a necessary amount of polymer P-2. Polymer Preparation Example 3 Polymer Preparation Example 1 was subjected to the same polymerization and post-treatment, except that 2 100 g of glycolide was replaced with 200 g of glycolide and 10 g of L-(-) lactide to obtain Glycolic acid-lactide copolymer (Polymer P-3). The same method was repeated to prepare the necessary amount of polymer P-3. Polymer Handan Example 4 L-(-) lactide (manufactured by Tokyo Chemical Industry Co., Ltd.) K ethanol was recrystallized and refined. 210 grams of refined L-(-:) lactide was filled into a cylinder made of PF A, blown with nitrogen, and dried at room temperature for about 30 minutes. Secondly, 0.03 g of tin octoate as catalyst was added, and nitrogen was blown to maintain polymerization at 130 C for 10 hours. After the polymerization was completed, the cylinder was cooled to room temperature, and the rosette polymer was taken out from the mash, pulverized to fine particles at about 3 mm, and dried under reduced pressure at about 100 t: and about 0.1 kPa. One night, the remaining monomers were removed to obtain polylactide (polymer CP-1). The same method was repeated to prepare a necessary amount of polymer (CP-1). Example 5 of polymer blending Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and polymer blending Example 1 The same polymerization and post-processing, but without the catalyst Sn C 1 4 6 .5 Η 2 0, polyglycolic acid ( Polymer CP-2). Repeat the same method to prepare the necessary amount of polymer CP-2. The physical properties of each polymer obtained from Polymer Preparation Examples 1 to 5 are shown in Table 1. -19 — The size of this paper is applicable to the national treatment of China. Bu \ s Grid (2IOX W7 public money) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 4 05 7 6 A7 B7 V. Description of the invention (18) [Table 1 ] Polymer Preparation Example 1 2 3 4 5 Polymer Composition G1) (wt / wt) GA GA / EX- = 95/5 GA / LA = 95/5 LA-· GA Polymer No. P-1 P ~ 2 P-3 CP-1 CP-2 77 * (Pa s) 440 390 420 320 27 Natural s giant Tg (X) 38 38 38 53 37 Tc 1 (t;) 83 77 74 105 80 Tπ (TJ) 220 214 215 175 220 Δ Hm (J / g) 71 64 67 51 73 Density of crystals (g / cm 3) 1.58 1.57 1.56 1.26 1. 58 () :: 1) GA = glycolide, EX = ethyl oxalate, LA = L lactide (please read the notes on the back before filling this page) I &gt; Binding and binding The paper size applies the Chinese National Standard (CNS) Λ4 grid (21〇κ2 () 7mm) V. Description of the Invention (19) Α7 Β7 Printed by the Consumer Cooperative of the Central Standards Bureau, Ministry of Economic Affairs, Example 1 Take polymer P-1 under a nitrogen stream and supply it to a small biaxial kneading extruder equipped with a 3 mm 彡 nozzle &gt; Melting temperature about 2 30-- 235, K strands are discharged and cold cut to obtain pellets (N 0 + 1). This pellets (N 0. 1) are supplied to the injection molding machine. The cylinder temperature is 2 30 r, the metal model temperature is ioor, and the injection pressure is 49 MPa. The injection conditions are formed into a test piece for measuring physical properties. The molded article is annealed at 150 ° C for 10 minutes. 9 An injection test piece (Ml-1) is obtained. Example P, 100 parts by weight of polymer (P -2). Add Jue fiber (diameter 20 μ length 0.7m Π1 * Wu Yu Chemical Industry Co. M -1 07T) 5.0 parts by weight, and inorganic boric acid 0.1 parts by weight * make the cylinder temperature about 2 2 5--2 3 0 ° C., Yuhe Example 1 »Modified granules (N 〇. 2) 0 Using this granules (ti 〇. 2), the same as in Example 1, except that the cylinder temperature is about 2 2 5 to produce injection molding tablets (M2 -1) 〇W Example is the same as Example 1, except that the polymer P- 3 10 0 parts by weight is added with oxidized sand powder 0.1 weight * The cylinder temperature is about 2 2 5 ^ -230 V, the modulation particles (N 0. 3) 0. Using this particle (N 0. 3) 1 is the same as in Example 1, except that the cylinder temperature is about 225 10. Model sheet (M3 -1) [Comparative Example 1 and Example 1 are the same &gt; except that the polymer CP -1 t Cylinder '&gt; obtained from Polymer Modification Example 4 is used (m degree approx. 185--1 9 0 ° c modulation Granules (N 〇. C 1): * Use the granules (N 0, C 1), and implement the same 洌], but the cylinder temperature is about 1 8 5 r -2 1- This paper size applies to the Chinese National Standard (CNS) Λ4 is i 2: K) ^^ 1 ^^^ 1 Im 'Shi 4H ^^^ 1 ^^^ 1 (nl nn ^^^ 1 ^^^ 1 nf (Please read the precautions on the back before filling in this Page) d _B7__ 5. Description of the invention (20), injection molding H (MC Bu 1) is obtained. hh is the same as in Example 2 except that the polymer (C P-2) obtained in Polymer Preparation Example 5 was used to prepare particles (No. C 2). Using this pellet (N 0. C 2), as in Example 1, a molded sheet (MC 2-1) was injected. f: h m m ^

Same as in Example 1, except that the injection molding cylinder temperature was set to 260 ° C, and injection molding was attempted, because the polymer was severely decomposed during the injection, and the normal injection of the molded product was not terminated. Using each of the injection molded sheets obtained in these Examples and Comparative Examples, the physical properties were measured, and the results are shown in Table 2 in summary. (Please read the precautions on the back before filling out this page) I — Binding _ Printed. Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-2-This paper conforms to the X · degree General National Standard (CNS) Λ4 specification ( 210X297 public box) 44 05 7 6- invention notice (21 A7 B7 printed by the Central Consumer Standards Bureau of the Ministry of Economic Affairs Consumer Cooperatives [Table 2] Examples Comparative Examples 1 2 3 1 2 3 Polymer No. P-1 P-2 P-3 CP-1 CP-2 P-1 Composition as additive type—Carbon fiber anhydrous boric acid silica——Adding amount (parts by weight) —5.0 0.1 0.1——Particle number 1 2 3 C1 C2 1 Injection molding Physical properties X Zode strength (kJ / m 2.) 43 45 41 10 3-Buckling strength (MPa) 220 220 200 80 30-Buckling elastic coefficient (GPa) 6.8 6.9 6, 2 3.5 6, 2 Tensile strength (MPa ) 130 140 125 50 30 One elongation (¾) 18 13 18 5 3 Disintegrability in the soil Yes Yes Yes Yes --- Dian Kao Sister Cheng Wu Sister Cheng Wu molding stopped (Please read the precautions on the back before filling in this Page) installed. -Φ This paper ft scale applies to China National Standards (CNS) Λ4 specifications (2 丨 0 Kimio)

Claims (1)

X 一 ii _______— nr 3 VI. The scope of patent application is too productive 丨 #u 丨: 1 charge ... Patent No. 86105140 "1ΓZΓ Alcohol-Acid Projectile and Its Preparation Method" (Amended on January 11, 1990) The scope of A's patent application: 1. A polyglycolic acid injection molded product consisting of 70% or more of glycolide containing repeating units shown in the following formula (I), and a product selected from the group consisting of vinyl oxalate, lactide, lactones, Trimethylene carbonate and at least one cyclic copolymer army of 1,3-dioxane repeating units of less than 30% by weight:-—0—ch2—c—- I! ⑴ _ 0_ (a) melt Viscosity 7 / * [Temperature (melting point Tm + 20 ° C), Shearing speed 10,000 / sec. Measurement] is 100 ~ 5,000 Pa · s, (b) Melting point Tm is above 150 ° C, & lt c) A thermoplastic resin material with a melt heat content of ΛΗπι above 20 J / g, and (d) a non-oriented crystal with a density of more than 1.50 £ / cm3, is molded at a temperature range of injection temperature Tin ~ 255t Person 6 2. If the injection molding of item 1 of the patent application scope has disintegrability in soil. 3. If the injection molding of item 1 in the patent application scope, the Izod impact strength (no gap, 25 &quot; C) is above 20kJ / ra2. 4. For the injection molded product in item 1 of Shen Lili, the tensile strength is above 60MPa and the tensile elongation is above 5%. This paper size is applicable to China National Standards (CNS) Λ4 specification (210X 297 mm)-&lt; --'------ ^ ------ order ------ line. (Please (Please read the notes on the back before filling in the negative) (Ministry of Economy and Intellectual Property, 4 / .7, Lagongxiao #Cooperative Society Prints the Ministry of Economics Smart Finance Chaos / ¾¾Printed by the Consumer Cooperative Cooperative A8 B8 CS D8 Garden 5. If the injection molding of item 1 of the scope of patent application has a buckling strength of 100 MPa or more and a flexural elastic coefficient of 5 GPa or more. 6. If the injection molding of item 1 of the patent application scope, the thermoplastic resin material is composed of a polyglycolic acid monomer. 7. If the injection molding of item 1 of the patent application scope, the thermoplastic resin material is polyglycolic acid. And at least one composition selected from the group consisting of inorganic materials, other thermoplastic resins, and plasticizers. 8. If the injection molding of item 7 of the patent application scope, the thermoplastic resin material is polyglycolic acid, and a composition selected from the group consisting of inorganic materials, other thermoplastic resins, and plasticizers, relative to 100 weight of polyglycolic acid Parts, the composition contains 0 to 100 parts by weight of inorganic materials, 0 to 100 parts by weight of other thermoplastics, and 0 to 200 parts by weight of plasticizers »9. If the injection molding of item 8 of the scope of patent application, The thermoplastic resin material is a composition containing 0.01 to 50 parts by weight relative to 100 parts by weight of polyglycolic acid. 10. If the injection molding of item 9 of the scope of benefits is applied, the thermoplastic resin material is 100 parts by weight of polyglycolic acid, and it contains a composition of 0.05 ~ 10 parts by weight of inorganic material-11. The injection molding of item 1 in the scope of profit, in which the polyglycolic acid is a separate ring-opening polymer of glycolide. 12. For example, the injection molded article in the scope of application of patent No. 1, wherein polyglycolic acid is a copolymer of glycolide and ethylene oxalate. -2- This paper size applies to China National Standard (CNS) A4 specification (2 丨 0 &gt; &lt; 297gongchu) ----, ----------- ΪΤ ------ • /-(Please read the precautions on the back before filling in, κ) Ministry of Economic Affairs Clear General Finance-; /.;: «Printed by Industrial and Consumer Cooperatives 6. Scope of Patent Application 13. If the scope of patent application is the first A molded product in which a polyglycolic acid-based glycolide and lactide copolymer is used. 14. A method for producing a polyglycolic acid injection molded product, which is characterized in that ethyl acetate containing a repeating unit represented by the following formula (1) is used. 70% by weight or more of lactide, and 30% by weight or less of at least one cyclic comonomer selected from vinyl oxalate, lactide, lactones, trimethylene carbonate, and 1,3-dioxane Repeating unit: —0 — CH2 — C —- II (1) _ 0 _ (a) Melt viscosity [temperature (melting point Tra + 20 ° C), shear rate 1,000 / sec. Measurement] is 100 ~ 5, 000Pa · s, (b) Melting point Tm is above 150t, (c) Melt heat content △ Hra is above 20J / g, and (d) Non-oriented crystals have a density of 1.50g / cra3 or higher for polyglycolic acid. Thermoplastic resin material Into the particles, emitted to the mounting for the eaves molding injection molding of Jin Yang model, at a cylinder temperature Tra~255 t 'square metal mold temperature ° ~Tra, injection pressure 1~104Mpa emitted by molding. 15. For example, the manufacturing method of item 14 of the patent application diagram is based on a cylinder temperature of 150 ~ 255TC, a metal model temperature of ~ 190TC, and an injection force of 10 ~ li ^ MPa. 16. If the scope of patent application is item 14 The manufacturing method is after the injection molding, the crystal is -3- This paper is up to the standard of China National Standard (CNS) A4 (210X 297 mm) I IJ. —-- * ------------ Order (Please read the notes on the back before filling in 4¾) Temperature Tc, ~ Tra temperature annealing 1 minute shovel to ίο hours. 17. According to the manufacturing method of the scope of application for patent No. 14, in which the pellets made of thermoplastic resin are supplied with thermoplastic resin material to the uniaxial or biaxial roof eaves and melt-mixed in the temperature range of Tnj ~ 2551C, pressed into strands, Winner of the stock cut (please read the precautions on the back before filling it out). Wisdom of the Ministry of Economic Affairs 4 ^: Printed only by the Consumer Cooperative Cooperative-4-Wood and paper are suitable for China National Standard (CNS) Λ4 specifications (210X 297 mm) X 一 ii _______— nr 3 VI. The scope of patent application is too productive 丨 #u 丨: 1 charge ... Patent No. 86105140 "1ΓZΓ Alcohol-Acid Projectile and Its Preparation Method" (Amended on January 11, 1990) The scope of A's patent application: 1. A polyglycolic acid injection molded product consisting of 70% or more of glycolide containing repeating units shown in the following formula (I), and a product selected from the group consisting of vinyl oxalate, lactide, lactones, Trimethylene carbonate and at least one cyclic copolymer army of 1,3-dioxane repeating units of less than 30% by weight:-—0—ch2—c—- I! ⑴ _ 0_ (a) melt Viscosity 7 / * [Temperature (melting point Tm + 20 ° C), Shearing speed 10,000 / sec. Measurement] is 100 ~ 5,000 Pa · s, (b) Melting point Tm is above 150 ° C, & lt c) A thermoplastic resin material with a melt heat content of ΛΗπι above 20 J / g, and (d) a non-oriented crystal with a density of more than 1.50 £ / cm3, is molded at a temperature range of injection temperature Tin ~ 255t Person 6 2. If the injection molding of item 1 of the patent application scope has disintegrability in soil. 3. If the injection molding of item 1 in the patent application scope, the Izod impact strength (no gap, 25 &quot; C) is above 20kJ / ra2. 4. For the injection molded product in item 1 of Shen Lili, the tensile strength is above 60MPa and the tensile elongation is above 5%. This paper size is applicable to China National Standards (CNS) Λ4 specification (210X 297 mm)-&lt; --'------ ^ ------ order ------ line. (Please (Please read the notes on the back before filling in the negative) (Ministry of Economic Affairs, Zhi Zongcai, 4 / .7, Lagongxiao # Printed by Cooperative