TW533219B - Degradable polyurethane resin - Google Patents

Abstract

The invention is a degradable polyurethane resin obtained by reacting 2,5-/2,6-diisocyanatomethylbicyclo[2.2.L]heptane and/or a modified compound thereof with polyol comprising a single compound, mixture or copolycondensate selected from the group consisting of (A) polyhydroxycarboxylate polyol, (B) aliphatic polyester polyol and (C) saccharides, or (D) straight or branched polyol formed by condensation of (A) and/or (B) with aliphatic polyhydric alcohol having functionality of three or more, and the polyurethane resin has hydralyzability and biodegradability, is excellent in rigidity and elasticity in combination with flexibility as compared with conventionally known biodegradable resin, and can provide formed articles having outstandingly high elasticity and elongation and other unprecedented properties.

Description

533219 V. Description of the invention (1) [Technical Field] The present invention relates to the use of 2, 5- / 2, 6-diisocyanatomethylbis% [2 · 2 · 1] heptane and / or The modified polyurethane is a novel polyurethane resin with a specific structure of the binding agent. More specifically, it relates to a novel polyurethane resin having decomposability, that is, hydrolytic (hydrolytic) and biodegradable properties, and its composition. Formed products. [technical background]

In recent years, the environmental pollution caused by plastic waste has become a worldwide problem. The biggest cause of this problem is that plastics such as polystyrene, polyvinyl chloride, and polypropylene, which account for most of the waste, are not biodegradable, so although they are buried in the soil, they remain in the original state. Due to. Furthermore, in the case of incineration, generally, the combustion heat of plastics is very large, and it also causes the combustion gas to be a cause of atmospheric pollution. Therefore, it is difficult to deal with only ordinary incineration equipment. Moreover, although recycling methods are gradually becoming popular, they are not suitable for recycling, and the field of gum utilization also accounts for a considerable part. Due to this situation, the development of biodegradable plastics that are likely to degrade in the natural environment is being developed. Many biodegradable resins have been reported, and the representative biodegradable resins are very well known, such as polyglycolic acid, polyhydroxypropionic acid, polyhydroxybutyric acid, polyvaleric acid, polycaprolactone, etc. The polyhydroxycarboxylic acids are aliphatic polyesters such as polybutylene succinate, polybutylene adipate and the like obtained by polymerization of polyhydric alcohols and polybasic acids. In addition, the use of the following substances is also being studied: polyamino acids such as polybutadieneimine, such as sugars such as molasses or cellulose and cellulose denaturants, chitin, polyglucosamine, etc. And its degeneration

Page 4

533219 V. Description of the invention (2) _ Body, such as gelatin or sericin, lignin resin coffin oil cage i ten Congsu protein-specific denatured origin from the town A natural oil derived from vegetable oil net, etc. . However, the use of conventional resins is reported to be qualitative, mechanical, or chemical in nature, and the required physical properties are sufficient as substitutes for conventional resins. In 3 = solvable ^ hydroxypropionic acid) is the only colorless and transparent, especially polyacrylic acid (polyurethane…), the material is a dissolving resin, although it shows its advantages in terms of tensile strength, but Although τ 舳 ^ is its disadvantage. In addition, there are many in manufacturing: 'or fragile resin with elongation'. Therefore, various designs have been made on its countermeasures. The burden (burden) is very large. Give a method for reacting a fatty acid vinegar compound. The example is low, and the cyanocyanate ester is reacted to obtain an aliphatic polyester = poly "and $ Iolite Kaiping 5-1 48352 and the like. Furthermore, / It is not disclosed in the polymerization of Japanese monohydric alcohols and polyacids =) that the di-aliphatic polyvinegar (the example of polyacid vinegar compounds is disclosed in Japan) =, the use of polyisocyanate, kaikai Η 577G3, etc., and the example of the combination of public esters of Erping No. 4- 1 89822 was disclosed in the Japanese version: Polysaccharide isocyanate hunting, etc. JP 9-302061 ϊ 虎 公 However, it is used in Polyisocyanate, | Right harmfulness is high, 'Moreover, the _: # —general;' It has environment In addition, the load is very large. Therefore, the use: shame also shows that it is natural S 荇 1 > π H 七 仏 田 ", the use of species to the natural environment is the same as the two: == ί ϊ 之 cool six Methyl diisocyanate or Isophor Bulletin, JP-A-H5-M75 Λ Kai-Ping ^ Hot, when using Liu Ya Rong 2 page 5 88ll6687.ptd 533219 5. Description of the invention (3) The following cases of isocyanate Disadvantages: That is, the manufacturing operability is deteriorated due to the high vapor pressure. Although a biodegradable resin with excellent tensile elongation can be obtained, the mechanical properties such as the drop strength and breaking strength of the resin are poor. On the other hand, 'different in use In the case of mono-isocyanate, because the reactivity of the two isocyanate groups is different from each other, the reaction speed is very low, that is, the burden on manufacturing is a disadvantage. &Amp; The purpose (task) of the present invention is In view of the shortcomings of the conventional technology, a novel resin with improved decomposability compared with the conventional biodegradable resin is provided, and a safety which is released from the natural environment is higher than that of the conventional technology. , and The load at the time of the reaction is small, and the hydrolyzable (hydrolyzable) and biodegradable resin is a degradable resin, and 2 is a molded product thereof. [Disclosure of the Invention] In order to achieve the above objective, the inventors of this case, The use of a diamine that is not equivalent to Nine, Fruit 1, 1, isomeric acid fluorenyl bicyclo [2.2.1] heptane (hereinafter Π, 1) as the polymer binder of the decomposable resin and di-lipid : Capture, surprisingly, you can get-a kind of maintenance: mentioning the biological properties of the two resins is the strength / resistance of the degradable resin, and the burden of manufacturing 彳 卩, gg ^ square buckle elongation or 0fcl ^ ° ^ /, the decomposable polyamines ^ μ Yue Yue said the same thing, so the present invention was completed. That is, the present invention includes: <: > A polyurethane resin having a decomposable property, and the lipid is composed of a polyhydric alcohol and formula (1) /, and $ lies in the tree.

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88116687.ptd Page 9 533219 V. Description of Invention (7)

The trimethylolpropane adduct or its block copolymer shown, and the formula (丨 〇)

OCN

/ NzzzCi ^ N

NCO (10)

(Wherein “z is an integer of 1 or more) one or two or more kinds of denaturants formed by the polycarbodiimide compound shown in the formula; < 9 > as described above < 1 > has decomposability Polyurethane resin, in which the amount of 2,5- / 2,6-diisocyanatomethylbicycloheptane and / or its modified form is 0.001 when the polyol is used as a reference 4〇wt „/ G; < 1 0 > as described above < 1 > ~ < 9 > polyurethane resin having hydrolytic property; < 11 > as above < 1> ~ ≪ 9 > Polyurethane resin with biodegradability;

&lt; 1 2 &gt;-a polyurethane resin raw material composition, characterized in that it contains as many το alcohols as above &lt; 1 &gt; and 2, 5-/ 2, 6 -diisocyanatomethyl Bicyclic [2 · 2 · 1] Glycogen and / or its denaturants · &lt; 13 &gt; A polymer film formed from the decomposable polyurethane resin of the above &lt; 1 &gt; Or &lt; 14 &gt; a ΛKK compound sheet made of the decomposable polyamine of the above-mentioned <丨 &gt;

Page 10 533219 V. Description of the invention (ίο)

(2-2) (In this equation, R1 represents an alkylene group having 1 to 4 carbon atoms in a straight chain portion and an alkylene group having 1 to 6 carbon atoms in total including a branched alkyl group, furthermore, R2 represents an aliphatic hydrocarbon group having a substituent of 2 to 20 carbon atoms, and a and b are integers of 1 or more). In the case of formula (2), formula (2-1) and formula (2-2), R1 in each formula is, in detail, a methylene group having a carbon number of 1, or a carbon number of a linear portion being 1 And the alkylene group substituted with fluorenyl, ethyl, or propyl, or the carbon number of the linear portion is 2 and the alkylene group substituted with methyl or ethyl, or the carbon number of the linear portion is 3 and substituted An alkylene group having a fluorenyl group, and in this equation, R1 may be the same, or a copolymer including two or more kinds of structural units may be used when m in the formula is 2 or more. It is an aliphatic polyhydroxycarboxylic acid, which serves as a raw material of the aliphatic polyhydrocarbon carboxylic acid oligomer or polymer represented by the formula (2). Specific examples thereof include glycolic acid, glycolic acid, 2- Hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 2-hydroxycaproic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid , 2-hydroxy-2-methylbutanoic acid, 2-hydroxy-2-ethylbutanoic acid, 2-hydroxy-2-methylvaleric acid, 2-hydroxy-2-ethylvaleric acid, 2-hydroxy-2 -Butylvaleric acid, 2-hydroxy-2-methylhexanoic acid, 2-hydroxy-2-ethylhexanoic acid, 2-hydroxy-2-propylhexanoic acid, 2-hydroxy-2-

88116687.ptd Page 13 533219 V. Description of the invention (12) (3)

H0-R2-0H glycols. In the formula (3), R2 represents a month having a carbon number of 2 to 20 and can have a substituent; an aliphatic hydrocarbon group is a diol represented by the formula (3), and specific examples include ethylene glycol, Glycol Λ Glycol), Di-t (ethylene di-K, π-green. Di (ethylene glycol), propylene glycol, mono-glycol, 1,4-butanediol, 3-methyl-1,5 Monopentyl 1'9 nonyl alcohol, neopentyl glycol, polytetramethylene glycol, monopyridine (acetamidine (propylene glycol), 1,3-diol, 1,6-hexanediol-one., ...-appeal , Chengtei τdiol, 1,4-cyclohexane dimethanol, etc. One or two or more kinds of glycols can be used. Among them, based on the ease of obtaining the goods and the use of f Ethylene glycol,!-, 4-butanediol, and 4-monocyclohexanedimethanol are relatively low. However, Asia is not limited to these exemplified compounds, which are mainly available, and are not particularly limited. Furthermore, It is also possible to use other polyhydric alcohols. J "M will again be the aliphatic polybasic acid shown in the formula (4). In formula (4), +- Acid, pimelic acid, One can use one or more aliphatic hydrocarbon groups of neutral dodecanedioic acid and cis. It is represented by formula (4); the lipids which can have substituents such as ethanedioic acid and succinic acid: ... Specifically, polybasic acids such as suberic acid, azelaic acid, sebacic acid, glutaric acid, adipic acid, fumaric acid, and the like are exemplified in the apparatus, and the 2 'state is The anhydride or ester is also T, and then *,, or two or more types are not necessary. J: It is possible to form an aliphatic: ^ Limited to this and to the limit., I § Japanese acid raw materials

88116687.ptd 15th stomach ^ 3219 V. Description of the invention (13) It is the easiness of the above-mentioned (B) aliphatic polysacral __, and the production of ~ 70 alcohol, the price and availability of its raw materials are available. From the viewpoints of the softness of the resin of polyethylene succinate, etc., the purpose, polybutylene adipate§, purpose, and so on, succinic acid purpose, polyethylene adipate Adipate, etc., are used as the glycol butadiene adipate and polybutylene glycol. Specific examples of saccharides, polysaccharides, and / or agricultural products = early sugars, disaccharides, and oligosaccharides include erythritol, 7-iso, and denatured species. For example, monosaccharides such as lyxose, Allose, Alchoose? ; Dioscorea gum, xylose, duose, galactose, tyrolose, fruit 1 digalactose, gulose, maltose, galactofuranose, gum piperanose, ::: Sugar, grape furan, ribose, sugar, sedulone heptane, deoxymannose, = sugar: amine sugar, galactosamine and the like. These sugars, regardless of the ratio of the substances in them, can also be disaccharides, polyacetates composed of one or two or more kinds ... thought of enolates, oxides, three substances, sugar cane, etc. The modified form 'x can also be a mixture or molasses.

Of course, the sugars used in the Ming Dynasty can also be cellulose X, cellulose nitrate, cellulose acetate, ethyl cellulose, celluloid, mucus, regenerated cellulose, saponin, copper ammonia, which are formed by long chains of monosaccharides. Rhenium, cupro-ammon rayon, cupro-ammonia film, Bemberg (a regenerated cellulose fiber), hemicellulose, starch, gum arabic, guanhua bean gum, locust bean gum, ak, sago-gum ( acasia gum), chitin, chitosan, etc., or their variants may be mainly used as a polysaccharide alcohol, and are not particularly limited. Another 1

88116687.ptd Page 16 533219 V. Dicarbonyldiimide or block copolymer of NBDI shown in the description of the invention (17), formula (8)

The biuret of NBDI or its block copolymer shown in formula (9)

The three propylene diene adducts or block copolymers of NBDI shown in the figure, and the formula (10)

OCN

/ NzzzCi ^ N

The NBDI tripolycarbonyldiimide shown in NCO (10) (where z is an integer of 1 or more) is better in terms of ease of synthesis and availability, but is not limited by these examples. Furthermore, two or more compounds of NBD I and / or its modified form may be used simultaneously.

88116687.ptd Page 20 533219

V. Description of the invention (18) In the present invention, the above-mentioned polyol can be reacted with NBDI to obtain a decomposable polyurethane resin having a target substance, but the method is not particularly limited. At the time of the reaction, it is also possible to perform anti-homogeneity in the presence or absence of a solvent and the reaction in the presence or absence of a catalyst, and the reaction temperature may also be determined according to the skill of the raw material. !) 丨 The remaining properties of its modified form 'or the physical properties of the polyhydric alcohol used in the present invention, or the properties of the polyurethane resin that can be obtained, should be appropriately adjusted.

^ The amount of NBDI added at the time of application can be changed according to the name of the polyol used in the present invention ^ s or the number of terminal functional groups or the desired physical properties, so it is not particularly limited, but usually based on the reaction _ When the total weight is used as a reference, it is 0.001 to 40% by weight, 0.001 to 25% is better than…, more preferably 0.001 to 10% by weight, and most preferably 0.001 to 5% by weight. If the added amount exceeds 40% by weight, there may be cases where the alcohol is not sufficiently mellow. If the added amount is less than 0.001%, the effect may be almost completely lost. The reaction is in% of the life medium used, which can be used as a solvent. Stupid, methylbenzyl, dibenzyl, and trioxine. For example, 4 r ^ ^ a beetle, o-dichlorobenzene, -qi.

Alkane, Lice imitation, Carbon tetrachloride, Dioxane, Tetradone 7 Tetrahydrofuran, 1,4-Dioxolane, N, N ~ Dimethyl A :, Tetramethylacetamide, N-methyl -2-Roar slightly bite _ m, 3 methylene terephthalate, N /-dimethyl dimethyl sulfonium, sulfolane, etc., are not particularly limited to tertiary hydroimidazole a made of soil. Furthermore, the catalyst was used to catalyze the catalyst Cut mouth, a corner that can be used]

533219 5. Description of the invention (19) Specific examples of amine, 1,4-ethylamine and the like include dibutyltin dilaurate and tetramethyl. Nitrogen [2, 2,2] bicyclic octane, tin octoate, 4 ~ methylmorpholine one. But it is not particularly restricted. In addition, the ^ of the urethane catalyst is compared with the known amount of carbamic acid ...

limit. ~ ~ Lord J again

In the present invention, the reaction temperature also depends on the type of the above-mentioned polyhydric alcohol or the produced urethane formic acid Sl resin. For this purpose, there is no particular limitation, but ^ in the absence of a solvent, the reaction is performed under molten conditions, so ~ 2 The reaction was performed in a temperature range of 50 ° C. In addition, the presence of a solvent usually proceeds in a range from room temperature to the boiling point of the solvent. In the present invention, a polyol can also be reacted with NBDI to prepare a prepolymer, whose polymer chain ends substantially become isocyanate groups, and the iron sable is reacted in one step to make a decomposable polyurethane g. Purpose resin. For example, it is also possible to react a linear aliphatic polyester polyol with I to form a substantially isocyanate-terminated terminal, and then to form an amine ester in the presence of water, or to form a carbodiimide. In the presence of the catalyst, a biodegradable polycarbodiimide is formed. By forming a foam, a foamable polyurethane having a decomposable or biodegradable property can be obtained. ’

As described above, the polyurethane resin of the present invention has a urethane bond produced by the reaction of the above-mentioned polyol and NBDI in the resin structure, and also has a urea bond, Bonds such as amine bond, carbodiimide bond, urethane bond, diuret bond, isocyanurate bond, isocyanide carbodiimide bond, fluorenimide bond, etc., but are not particularly affected limit. The existence of these bonds depends on the type of NBDI and / or its modification, or more

533219

Yuan alcohol has the officer ## 夕. The type of the b group or the reaction conditions can be arbitrarily selected. For example, in order to obtain a polyurethane resin having a heterotrimer decomposability, a compound is used as a raw material, or a terminal functional group may be made into an isocyanate group beforehand. The reaction is carried out to produce a biodegradable polyurethane resin cyanate bond with decomposability and biodegradability. The isocyanate polyol of NBD I can be reacted with NBD I to make Decomposability of an esterification catalyst having a heterotrimeric ester bond. In particular, in the present invention, the obtained polyurethane resin having decomposability is not known as a biodegradable resin having a conventional biodegradable resin. It has hardness, but at the same time shows excellent elasticity or softness, and is given heat resistance and chemical resistance in specific bonding methods such as carbodiimide bond and fluorenimine bond, so it can also be used as decomposability. And the development of new uses for biodegradable resins. The excellent decomposability of the polyurethane resin of the present invention refers to the phenomenon that it becomes soluble in water due to hydrolysis by the action of an acid or an alkali aqueous solution. For example, it usually means that a powdered resin has In an aqueous solution with sufficient alkali content, it will decompose and change within 72 hours (preferably within 24 hours, and more preferably within 5 hours) at a temperature ranging from room temperature to 100 ° C. In terms of water-soluble state. Also, the sufficient amount of the test ingredient is usually more than the mole number of the structural unit of the resin. Furthermore, 'biodegradability' refers to the phenomenon that hydrolysis occurs in the natural environment due to the catalyst action of the hydrolysis enzymes of microorganisms and decomposes into water and carbon dioxide. In addition, in the present invention, the reaction rate ratio of NBDI and / or its denaturants is

88116687.ptd Page 23 ^ 3219 V. Description of the invention (21) Isophorone diisohelium is a small burden for sand-breeding. This is an excellent operation when it is manufactured ... At the same time it has two: the decomposable resin has a strong However, the polyamino acid T of the present invention is used for various applications. In addition to films, polymer sheets, and trees, they can be used for purposes other than the use of polymers as thin materials, or fibers for the purpose of general lengthening fibers, non-woven fabrics, porous ^ for purposes such as: short fibers , Incubator 'Food tray, wrap: Trash bags, soil bags, sponges, bottles &quot; and water tablets: ΐ, mold 1 spoon', seeds, cups, substrate, polymer fiber bundle / ^ ^ Multi-layer bags used in industry, coating materials for dish boxes, paper, etc., and materials used in layer factory materials; appliances for cigarettes, composite semi-permeable membranes, fractures, etc.) Clothing, surgery The JLJL is used for loyalty 4, support, or bone bonding materials, women's equipment or grafts for transplantation, fishing lines, and connection. Pot, nail polisher, pumice for bath, garden, Λ, bone capsule or container and packaging, fragrant micro glue ^ ^ is made of material, deodorant micro shrink film, adhesive, hot melt adhesive cape: Second, packaging, labeling, holding purple packaging tape, adhesive tape, back: containers, films, masking for painting, glasses frames, etc. The decomposability of the thin polyurethane resin used in the% sacral resin can be used as a biodegradable resin &lt; I urethane resin by making full use of the excellent physical properties of the present invention ^ ^ Broadly

88116687.ptd 111 Page 24

533219 V. Description of the invention (22) ____ For the above purposes.

In the present invention, in particular, the biodegradable polydiene obtained from I has the transparency of the reaction between aliphatic hydroxycarboxylic acid and NBDI. Regarding packaging materials such as formate resins, it has strong toughness, sheet materials, and dishes. The base material of the box, or the surface becomes an excellent polymer film, and the polymer polyurethane resin is the material of the base plate and the base material. Furthermore, the present invention is a clothing fiber or a non-woven fabric 2 / fiber that exhibits a soft texture, and is suitable for use as a base material for a 5 material 'disc box or a polymer film or a polymer molded article. Card base material rolling method, calendering method, etc. For its production method, for example, a solution flow solvent may be used. For example, when aerosol is used and the production is performed by a liquid casting method: Ketone, 1,3-dimethylformic acid amine, dimethyl sulfite, and 1-methyl-2-fluorene are cast on a smooth surface. The solvent used is not specifically removed, so that the implementer, as ^ ^ if you pay to the limit. One hundred and one times, in the Yuan line $ ^ # method, inflatable expansion method and so on. Regarding extrusion, the types of resins that can be manufactured using the conventional T-die differ, and =, because the melting temperature is within the range of 100 to 28 Gtm as desired. If it is equal to the limit, it usually has stability of molding and low overload probability. If it is difficult to obtain, polymer decomposition may occur. If the molding temperature is high, the degree will decrease, and coloring will occur. . The decrease in the molecular weight of X is stronger than the polymer film or polymer related to the present invention, or it can be extended, but in order to increase the rigid sound :, and the like are unextended X, forming and working, machinery 88116687.ptd page 25 533219 V. Description of the invention (23) For strength, hardness, impact strength, dimensional stability, bending resistance, etc., it is best to apply one-axis extension or two-axis extension to the obtained film or sheet. In the case of one-axis extension, it is usually extended from 1 to 1 to 5 times in the longitudinal or transverse direction. It is possible to execute the extension of the first axis and the extension of the second axis sequentially or simultaneously at the% combination of the two axis t extension.爨 The elongation temperature is different depending on the structure and composition of the polyurethane resin used. Therefore, it is not particularly limited, but the polymer's Tg (glass transition: shift) to (Tg + 5 0 ° c) range Inside is better. Above this temperature range-\ -mmL 售 局 温 日 守 ’sometimes cannot find the effect of increasing the strength caused by extension. Furthermore, the obtained molded article may be heat-treated at a temperature of Tg or more and less than "I · melting point" after molding. The heat treatment time is usually i seconds to 30 minutes. In the present invention, 'the obtained polyurethane resin is processed into a molded product_7. It can also be a mixture or a compound formed with other resins.' A, such as a light stabilizer, a plasticizer, Additives such as anti-oxidants, hot-filled S fillers, color inhibitors, and pigments to further improve physical properties.

Into: 'top: ί 5 Γ method can obtain the polyurethane resin of the present invention and = two "due to its hydrolyzability, it is subject to π = lt #knock or hydrolyzed in an alkaline aqueous solution for the desired purpose, or Decomposed (biodegraded) by the action of natural environment. The so-called biological tremor H dagger of the present invention ^ ^^ MtIS0 / CD148! The degree of decomposition calculated from the amount of emulsified carbon produced

533219 Description of the invention (24) They reach 60 / on the 7th day of the month. Above the resin. It is generally believed that after 3 months: resins with a degree of decomposition of more than 60% are resins lacking biodegradability. Second, when the compost is disposed of or is discharged, a bad condition occurs. Furthermore, the decomposable polyurethane resin raw material composition of the present invention is a composition containing the above-mentioned &lt; 1 &gt; polyol and NBDI and / or a modification thereof, and is heated or added with a contact such as When the compound related to the initiation reaction of the vehicle is used, it can be made into the polyurethane resin of the present invention.

When this composition is based on 100 parts (weight 1) of the polyol shown in (4) to (D) of the above <1>, the amount of NBDI and / or its denatured body may also be 〇 · 〇0 1 ~ 70 parts by weight, more preferably 〇1 ~ 3 〇 parts (weight), and more preferably 〇J ～ 1 〇 parts (weight), while containing aliphatic The polyhydric alcohol is preferably a biodegradable polyhydric alcohol, and its content may also be 0 ~; [0000 parts by weight, preferably 0 to 300 parts by weight, and more preferably 0. ~ 1 ο 〇 parts (by weight) is more preferable. In addition, additives such as a catalyst, a foaming agent such as water or an inert gas, a light foaming agent, a plasticizer, an oxidation inhibitor, a heat stabilizer, a filler, a coloring inhibitor, and a pigment may be contained. If the content of NBD I and / or the modified product thereof is less than 1 part by weight, the reaction for forming a urethane bond may be insufficient. Here, the aliphatic polyhydric alcohol refers to the thing exemplified above. It may be contained in the polyurethane resin raw material composition having biodegradability or not, and particularly In the case of more than 50 parts by weight, aliphatic polyhydric alcohols having biodegradability are preferred. [Examples] Hereinafter, the present invention will be described in more detail based on examples and comparative examples. But this

88116687.ptd

Page 27 ^ 3219 V. Description of the invention (25) :: Without being limited by these examples As shown in the synthesis examples and examples, a U-average molecule 詈 soldier ears / gram represents. The weighted average molecule 1 is determined by GPC according to the type of Zhaobiren 丨 廿 丄 + ΛKK compound. The head A knife is thin in the lice, and the average score is early; the acid value and the number of polyhydroxycarboxylic acids are flat. ^ M Ten spoons of molecular i are as follows. Lu Lujiayuan / Methanol 4 / 3 (volume ratio) of the solution: = glycol solution under the titration solution, using Baidong pz at N / 100f sodium / Jiashan soil mountain 〃. ⑺ using an automatic titration device to carry out titration, 瞀Calculate the number of carboxylic acids to obtain the acid value and the number ^ Synthesis Example 1 Yu Lizai "Using gas τ, implement one; mixer, thermometer, ~ Department &amp; After 1 liter of ventilation, ^ added the polyhydroxypropionic acid oligomer with a weight average molecular weight of about 3,000 and a number average molecular weight quantified by self-dehydration condensation and molecular weight of 1600, 〇 ^ Hydroxyl 0. ^ 0862 mole) and 300 g of methylene chloride to dissolve the former, followed by 2-chloro-1,3-di-f-imidazole ingot (hereinafter referred to as DM〇j 7. 48 g (0.103 mole) Ear), * 14—butanediol 90 lg (0 100 mol) was charged therein, and stone-formamidine 24.12 g (0.25 9 mol) was added. And stirred at 30 ~ 4 (rc temperature 3 Hours to carry out the reaction. After that, the reaction solution was washed with a 30% hydrochloric acid aqueous solution and water in this order. Thereafter, it was removed by heating under reduced pressure.

88116687.ptd Page 28 533219 V. Description of the invention (27) and water, in order to react in a positive and negative way, and then react to the liquid. Thereafter, the mixture was heated and removed under reduced pressure, and in a short period of time, 109 g of a polyhydroxypropionic acid modified polyester polyol was obtained. The soybean yield was 100%. The obtained seven take &quot; g has the weight average score obtained :: = f denatured polyester polyol (e) borrowed GPC / g 'is U8xi0-3 mole / g. In addition to synthesizing the second and the second L with the same molar ratio, three polyhydroxypropionic acids with an average weight of 1 L '1 0,0 0 (S), and 20,000 (h) were synthesized. Modified polyester polyol. 〗 Γ1-So: the hydroxyl value of the glycerol-modified polyester polyols from t to K hydroxypropionic acid are 1 · 2 1 x human two, 6 · 1 1 x 1 "4 mole / g, 3. 06 X 10-4 Mol / g. Synthesis Example 3 ^ ^ will be 1,4-丁

It is 8 85g of polyester acetic acid and tetraisopropyl titanate. ^ 一 w 又 υ uu ^ / enterprise, w and nana na, stomach g = ^ detachable flask (3 liters) equipped with a stirrer, fractional condenser, thermometer, and nitrogen V tg, under nitrogen 195 ~ 2 0 0 t in the air flow:. And b, and then a deglycolization reaction was performed under a reduced pressure of 0.6 Torr for 6 hours at 210 5 ° C. As a result, a succinic acid-based polyester (i) having an amount of f = average molecular weight of 17,000 was obtained. Cool to room ^ Butyric acid-based poly (i) is white, waxy and solidified. The valley point of this object is 11 0 ~ 11 5 t. ::-Butyrate per 750g, adipic acid 10.95g, and tetraisopropyl titanate 1.8g ^ It is possible to incorporate a device having the same equipment as the synthesis example of the above-mentioned polyester (丨)

533219 V. Description of the invention (28) Detachable flask (3 liters), perform esterification under nitrogen gas flow at a temperature of 1 90 ~ 200 ° C for 6 hours, and finally under a reduced pressure of 0.5 torr (torr) and The deglycolization reaction was performed at a temperature of 205 to 210 ° C for 7 hours. As a result, an adipic acid-based polyester (j) having a weight-average molecular weight of 15,000 was obtained. The adipic acid polyester (j) cooled to room temperature is cured with a yellowish butterfly shape. The melting point of this material is approximately 5 8 ° C. Synthesis Example 4 Synthesis of I-hydroxypropionic acid-denatured polyester polyols (k) to (m) Polyhydroxypropionic acid oligomer having a weight-average molecular weight of 3.0 g used in Synthesis Example 10.0 g (carboxyl group). · 0862 mol) and 300 g of dichloromethane were charged, the former was dissolved at 40 ° C, followed by the addition of 0.90 g (0.01 mol) of 4-butanediol and 17.48 g of DMC (( Kl03 Molar), and metoprolidine 24.12g (0.259 Molar), and then the reaction was performed at 40 ° C for 3 hours. After the reaction was completed, the reaction solution was diluted to 10%, and It was washed in this order with 30% hydrochloric acid and water, and this was concentrated by an evaporator to remove dichloropyrene. The weight average molecular weight of the obtained polyglycol diol (k) was about 30,000, and the molecular weight The degree of distribution and dispersion is 3.0. Except changing the use of 丨, 4-butanediol to 0.43 g and 0.347 g, repeating the same method as above to obtain a weight average molecular weight of 65,000 (1), 78 , 〇〇〇 (m) of polypropionic acid modified polyester diol. Examples 1 to 4 The weight average molecular weight obtained in Synthesis Example 1 was about 3,000,000. Hydroxypropylmethyl acid denatured polyethylene glycol purpose S (a) 100g of the flask was charged 2〇〇ml be hot-melt. In this period of about 30 minutes was added slowly stoichiometry of ...

533219 V. Description of the invention (29) N B D I 1 9 · 8 g (0 · 〇96 mol), hold for 1 hour to obtain a melting point of 17 q. 〇 Decomposable polyurethane (hereinafter referred to as polyurethane resin). Hereinafter, in Examples 2 to 4 and Comparative Example 1, the molecular weight of the polyester diol used was changed to 5,000 [polyol (b), Example 2], 10,000, respectively [ Polyol (0, Example 3), 20,000 [Polyol ((1), Example 4]) was used to synthesize a polyurethane resin. The weight average molecular weights of Examples 1 to 4 all reached 10 0, 0 0 0 or more. However, the amount of NBDI used is set to 0.5 mol times of the base number of the polyol. A pressed film having a thickness of 1 00 // m is made from the obtained polyurethane resin. The physical properties were measured. The physical properties of the obtained polyurethane &quot; ^ lipids are shown in Table 1. Example 5 is a polyester that is used in the same manner as in Synthesis Example 1 and has a molecular weight of 3, Polyhydroxypropionic acid modified polyester diol (a) of 0 0 0, 50 g of this polyester diol (a) and the heterodimeric acid acetic acid ester of NBDI can be made into polyester diol with the number of isocyanate groups. Fill the flask with the same number of moles as the hydroxyl group, heat it under a stream of nitrogen, and continue to stir under melting for one hour. This material is discharged on a stainless steel pad under nitrogen and To polyurethane resin. The physical properties of the obtained polyurethane resin are shown in Table 1. Example 6 Except for using carbonyl diimide of NBDI as a modified form of NBDI, Example 5 is used to obtain a polyurethane resin. The physical properties of the obtained polyurethane resin are shown in Table 1. Example 7 Except that the uretide of NBDI is used as a modified NBDI, Are based on

88116687.ptd Page 32 533219 V. Description of the invention (30) Embodiment 5 is implemented. The physical properties of the obtained polyurethane resin are shown in Table 1. Example 8 Except that trimethylolpropane adduct of NBDI was used for the NBDI denatured body, it was applied according to Example 5. Table 1 shows the physical properties of the obtained polyurethane resin. Example 9 was carried out according to Example 5 except that a carbodiimide having an average repeating unit number of 8 was used for the NBDI denatured body. Table 1 shows the physical properties of the obtained polyurethane resin. In addition, the obtained test piece of the polyurethane resin melt-molded at a temperature of 240 ° C has a heat distortion temperature of 7 ° C, and it exhibits good resistance to rubbing with a biodegradable resin. Example 10 ..., ▲ 100 g of the polyhydroxypropionic acid-denatured polyester polyol (e) having a weight-average molecular weight of 3,000 obtained in Synthesis Example 2 was heated to 2000 to melt it. :: Time to add 1 to the clock. The NBDI &lt; dropping amount is based on the final hydroxyl group of polyhydroxy: polyisocyanate, which can become a chemical isocyanate. Thereafter, it was allowed to stand for 1 hour, and was discharged under nitrogen to obtain a polyurethane resin. The results are shown in Table 1 in the same manner as in Example 1-t. ~: A weight average molecular weight of 5, obtained in Synthesis Example 2 was used. Q. The polyacrylic acid modified with propionic acid &amp; containing &quot;, 来 ,,,,,,,, and the like, except for Example 7, was implemented according to Example 10. The physical properties of the urethane resins are shown in Table 1.

88116687.ptd Page 33 533219 V. Description of the invention (31) Example 1 2 Except using the polyhydroxypropionic acid modified polyester polyol having a weight average molecular weight of 1 0,0 0 0 obtained in Synthesis Example 2, Example 10 was implemented. Each physical property is shown in Table 1. Example 1 3 Except that the polyhydroxypropionic acid-denatured polyester polyol having a weight average molecular weight of 20,000 obtained in Synthesis Example 2 was used, it was performed in accordance with Example 1. Each physical property of the obtained urethane resin is shown in Table 1. Comparative Example 1 After dissolving 100 g of polyhydroxypropionic acid having a number average molecular weight of 1,500 in 30 g of benzene, DMC13.52 g (0.08 mol) and stone-formamite I7.88 g (0 192 mol), after stirring for several minutes, let stand for 2 hours. 2 This solution is diluted to 丨 0%, and 30% hydrochloric acid and water are used in this order; diacid :: in a large amount of isopropanol, filtered and dried to obtain a polydioxine: ^ The physical properties of the knife are enough to confirm the physical properties. The polyhydroxypropionic acid was molded, and the results are shown in Table 1. From this result, it was obtained that the polyether hydration properties of the ester resin in the mechanical and physical properties of polypropionic acid as the base were not inferior: 爯 #hydroxypropionic acid, and furthermore, about the biological fraction of propionic acid obtained by molding =: Taking the person f, the polyhydroxy group obtained from Comparative Example 1 was broken, showing two sheets, which were only bent by 180 degrees. Comparative Dingba was not flexible. Will be obtained in the same manner as in Synthesis Example i.

88116687.ptd 533219 V. Description of the invention (32) __________ Xia 1 〇, ο ο 〇 polyhydroxypropionic acid modified poly ^ After heating to form a molten state, hexamethylene alcohol 1 〇 § was charged into the flask and added While continuing to stir for 1 hour. Although 2.44 g of methyl diisocyanate was charged, it was gelled. At the end of the reaction, the viscosity of the discharged resin increased rapidly, but no ester resin was formed. The obtained polyurethane = stainless steel pad was used to obtain a measurement of polyurethane properties, and the results were shown in a methyl ester resin to be molded to execute the polyurethane tree prepared in each of Example 4; furnace table 1 in. From this result, it was found that the polyurethane resin phase of the implementation was: '\ Compared with this, the biodegradability is consistent with Example 4 and is superior to this comparative example. There is no inferiority, and in terms of mechanical properties, ikj Example 3 will be obtained by denaturing the polyhydroxypropionic acid with the same formula as in Synthesis Example 1> and having a weight average molecule to heat to form After the molten state, 100 g of the diol (c) was put into a flask, and it was put into the flask, and the stirring was continued. Isophorone, diisocyanate 3.98g, it continues to stir for 6 hours and its viscosity increases very slowly,

Polyurethane resin. The two c pads were obtained: too solid :; compared with the polyurethane resin obtained in Example 4, the polyurethane resin obtained in Example 4 did not meet the drought resistance. In terms of physical properties, the examples 4 is superior to this comparative example. In addition, the polymer obtained by molding the mechanical polyurethane resin is another example of a polymer obtained by bending at 180 degrees and cracked once, showing that it is not flexible. It is only used

533219 V. Description of the invention (33) Table 1 shows the results of the biodegradability of Examples 1 to 13 and Comparative Examples 1 to 3 based on IS0 / CD1 485. Tensile test The biodegradable resins obtained in Examples 1 to 13 and Comparative Examples 1 to 3 were subjected to a tensile test in accordance with J I S K 7 1 1 3 and the results are shown in Table 1. Table 1 Degree of decomposition of biodegradable mechanical properties after 3 months% Breaking tensile strength MPa Elongation% Elasticity MPa Example 1 84 68 44 4110 Example 2 81 66 32 4800 Example 3 83 68 22 4230 Qin Example 4 82 70 21 4390 Example 5 80 77 18 6450 Example 6 83 66 17 4690 Example 7 84 67 61 4120 Example 8 82 68 33 4270 Example 9 79 72 11 4290 Example 10 83 69 28 4430 Common example 11 81 70 27 4240 #Example 12 85 73 30 4480 Example 13 84 73 32 4650 Comparative example 1 85 65 7 3380 Comparative example 2 83 39 35 3480 Comparative example 3 82 48 5 2130

88116687.ptd Page 36 533219 V. Description of the invention (34) Example 1 4 Put the polyester (i) 400 g and polyester (j) 100 g obtained in Synthesis Example 3 into a mixer, Fractionated condenser, thermometer, and a detachable flask (1 liter) of a nitrogen introduction tube, heated to uniformly melt, and brought the substance under a reduced pressure of i Torr (t0rr) for 10 minutes to restore normal pressure, For this purpose, 9.09 g of NBDI was added at a temperature of 200 C in a nitrogen stream. Although its viscosity increased rapidly, it did not gel. Stirring was continued for 30 minutes and it was drained onto a pad. From the obtained polyurethane resin, a pressed film having a thickness of 100 // m was prepared by a hot press. The toughness of this film is too high to be able to be applied by manpower

crack. Moreover, the tensile strength of the transparent film after extending three times in each direction is 75 MPa. X Through Example 15 5 300 g (1.43 mol) of 1,4-butanol and 354 g (3.0 mol) of succinic acid were put into a mixer, a fractionating condenser, a nitrogen introduction tube, and a thermometer. The flask (1 liter) was subjected to vinegarization for 5 hours at a temperature of 2000 to 2000 in a nitrogen gas stream. 'To this was added tetraisopropyl titanate 0.06 ^, and the condenser was changed to After the straight type, the deglycolization reaction was performed at a temperature of 220 t: and a reduced pressure of 0.5 Torr for 10 hours, and then discharged. The obtained polyglycol was white and hard-shaped because of its crystallinity. Its weight average molecular weight was 38,000, the acid value was 丨 · 〇2 X 10-5 mol / g, and the warp value was 5 88 XI 0-5 Mo / g. 100 g of the obtained aliphatic polyacetic acid glycol (hydroxyl value 5.88 × 10 ”mole / g) 100 § was charged into a flask (300 ml) equipped with a stirrer, a condenser, a nitrogen introduction tube, and a thermometer. After melting at 180 ° C., 77 g of NBDI was added thereto. although

533219

The stance increased rapidly, but the sub-gelation did not occur. After a while, let the anti-shore ^ hours end. Based on the obtained polyurethane, t, the reaction, ,, k, 1 1 ΠΠ々 two systems # to * amino ester resin by a hot press to make a sound: Eryi film, and the results of measuring physical properties, Stone skin breaking tensile strength H = a, breaking elongation is 4_, showing that its mechanical properties are good. L Γ 6g (Q, 10 moles) μ, 4 'butanediol 9.2g, DL—by 1

= g, methoxanthinic acid 0.05g, and toluene 40mi were charged into a four-necked flask (y0mu, and the dehydration condensation reaction was performed at a temperature of 100 ~ 11 (rc) for 7 days: wrong GPC did not show molecular weight results, The obtained number average molecular weight is 6,000, and the weight average molecular weight is 37,000. The warp value is iwx 10 mol / g. After that, 0.32 g of NBDI is added, and the reaction is performed at 10 (rc temperature d). 4 hours. The weight-average molecular weight at this time was 161,000. After the end of the reverse shoulder, toluene and sulfonic acid were removed under reduced pressure to obtain a denatured polybutylene adipate. Example 17 A polypropionic acid-denatured polyester diol (c) 50 g and dioxin 2000 g having a weight average molecular weight of 1 0,000 obtained in the same manner as in Synthesis Example 1 were charged into a flask. After dissolving it at a temperature of 100 ° C, NBD j 1.85g (8.95 X 10-3 moles) and 10 mg of diaza [2 · 2 · 2] bicyclooctane were added thereto. The reaction was carried out for 2 hours. Thereafter, 10 mg of 3-methyl-1 -phenyl-3-phosphlen oxid, which is a carbodiimide catalyst, was added thereto, and the reaction was performed at a temperature of 120 ° C. Reaction time is 20 hours. After finishing the reaction, it was cooled, but filtered, washed with 500 ml of methyl tert-butyl ether, and dried under reduced pressure at 80 ° C for 12 hours to obtain a decomposable polyurethane. Carbonized

88116687.ptd

533219 V. Description of the invention (36) Amine. This polyurethane resin was shaped by a hot press at a temperature of 240 ° C to form a pressed sheet having a thickness of 3 mm. Its Vicat softening point was 174 ° C as measured according to JISK 72 0 6. Example 1 8

40 g of cellulose acetate having a weight-average molecular weight of 110,000, 60 g of polypropionic acid-denatured polyester polyol (a) having a molecular weight of 5000 obtained in Synthesis Example 1, and 300 g of dibenzobenzene Fill the flask while at 120. 〇 Dissolve at temperature. To this, 1,4-diazine [2 · 2 · 2] bicyclooctane in 1% xylene solution lg was added, followed by NBDI Moore), and the reaction was continued J: h. After the reaction was completed, "cooling" was performed, followed by filtration, washing with isopropanol, and drying under reduced pressure at 8 ° C to obtain a polyurethane. The resin was molded into a thin film M, t, MP. ^ ^ λορλπ Table / Film-seeking system has a tensile breaking strength of 69 MPa, an elongation of 26.0%, and a tensile strength. Λ Those who performed a collapse stretching ^ raw modulus of 3920 MPa. The compound obtained in Synthesis Example 4 has 100 g of umbellic acid denatured polyester diol (k) to NBDI with a weight of 30,000 and a weight of NBDI of a knife amount of 30,000 are kept for 丄 hours, and are dissolved, and a stoichiometric ester resin is added to this. The polymer, at ^ your melting temperature ° C, gives a thickness of 800. The properties of the extruder equipped with a T die are shown in Table 2. 'Special film. The obtained film Example 2 0 Except using the polypropionic acid-denatured polyglycol diol (丨) obtained in Synthesis Example 4 and a weight average molecular weight of 65,000, the properties of the obtained film were all shown. Implementation according to Example 19. 9. Take in Table 2.

533219 V. Description of the invention (37) Example 2 1 Except the obtained Example 2 obtained by using polypropionic acid modification 2 In addition to the modification of polyhydroxysuccinic acid polybutylene succinate according to Example 1 9 Example 2 3 Hyaluronic acid denatured succinate dibutyrate was implemented. Except for the polyester polyester diol (m) having a weight average molecular weight of 78,000 obtained in Synthesis Example 4, 42 was implemented in accordance with Example 19. The physical properties of the film are shown in Table 2. The polyester polyester diol (1) having a weight average molecular weight of 6 5,0 0 and the diester having a weight average molecular weight of 50,000, obtained in Example 4 are mixed and used at a ratio of 9 0: 10. In addition, all roots are implemented. The physical properties of the obtained film are shown in Table 2. Polyester diol having a weight average molecular weight of 7,8,00 and polybutylene glycol having a weight average molecular weight of 50,000, obtained in Example 4 were used in accordance with a ratio of 80:20, both based on The physical properties of the films obtained in the examples are shown in Table 2. Mw ratio (X: Y) of Example X Breaking strength MPa, Example 1 9 10, 000 100: 0 64 Example 2 0 6 5, 0 0 0 100: 0 69 Example 2 1 78, 000 100: 0 73 Example 2 2 65,000 90:10 77 Example 2 3 78,000 80:20 82

Mw: weight average molecular weight X: polypropionic acid modified polyester diol Y: polybutylene succinate

88116687.ptd Page 40 533219

Example 2 4 In addition to the implementation of polypropionic acid, the fat was obtained by extrusion, but Example 2 5 was performed in addition to the polypropionic acid obtained in the second time, and Example 2 6 was modified to obtain a polypress. The urethane resin was prepared in the same manner as in Example 19, except that the ester diol having a weight average molecular weight of 3,000 obtained by the synthetically modified polyunstretched and unstretched polymer for unstretched and unstretched Example 4 was used. The obtained polyurethane tree was processed into an unstretched sheet having a thickness of 12 mm. Although the sheet was repeatedly bent at 1000 ° C for 1000 °, it was also flexible. Except for the ester diol (1) having a weight average molecular weight of 65,000 obtained in Example 4, all were carried out in accordance with Example 24. Although the sheet was repeatedly bent at 1000 ° C at 1000 ° C, its flexibility was also good. The procedure was carried out in accordance with Example 24 except that the hydrolysin-propionic acid-denatured polyester diol (m) having a weight-average molecular weight of 78,000 obtained in Synthesis Example 4 was used. The obtained unstretched sheet was broken after repeated bending at 89 ° C for 8 or 9 times, and the flexibility was also good. i 实施 例 2 7

In addition to the polyacrylic acid denatured polyester diol (1) having a weight average molecular weight of 65,000 obtained in Synthesis Example 4, and the polybutylene succinate having a weight average molecular weight of 50,000, Except for the ratio of 90:10, it was implemented according to Example 24. Example 2 8 Except for the polymer having a weight-average molecular weight of 78,000 obtained in Synthesis Example 4,

88116687.ptd Page 41 533219 V. Description of the invention (39) Hydroxypropionic acid modified polyester diol (m) and polybutylene succinate having a weight average molecular weight of 50,0 0 0 according to 8 0: 2 0 Except that the ratio is used, it is implemented according to Example 24. Example 2 9 A polyurethane resin was obtained in the same manner as in Example 19, and from the obtained polymer, melt spinning and fiber bundles were obtained using an extruder equipped with a spinning head. Use filament. The physical properties of the obtained filaments for the fiber bundles are shown in Table 3. Example 30 A polyurethane resin was obtained in the same manner as in Example 20, and from the obtained polymer, melt spinning and fiber bundles were obtained using an extruder equipped with a spinning head. Use filament. The physical properties of the obtained filaments for the fiber bundles are shown in Table 3. Example 3 1 Polyamine S resin was obtained by the same operation as in Example 21, and the obtained polymer was melt-spun, and the fiber was obtained by using an extruder equipped with a spinning head. Bundle with filaments. The physical properties of the obtained filaments for the fiber bundles are shown in Table 3. Table 3 Example X Mw Melting Temperature Tm ° C Tensile Elongation% Example 2 9 10,000 175 30 Example 3 0 65,000 172 40 Example 3 1 78, 000 173 40

88116687.ptd Page 42 533219 V. Description of the invention (40)

Mw: weight-average molecular weight X. Polyhydroxypropionic acid modified polyester diol G. Polybutylene succinate Example 3 2

20 g of the 5 sodium hydroxide aqueous solution of the polyurethane resin obtained in Examples 1 to 18 and the rotor were charged in a 5N ^ 10N: 'and temperature ~ 5 (rc temperature range using an electromagnetic stirrer to stir Based on the polyurethane resin powder of bismuth and bismuth, it is hydrolyzed and dissolved in water within a short time. "Raw" private bodies are [industrial availability] # ί :: ίf decomposable polymer The urethane resin is 2, 5 — / 2, 6-diisocyanatomethylbicyclo [2.2 tf. Or a modified form thereof, which is a decomposable resin, which is a kind of 5 compounds. Polyurethane hydrolysate of the binder = decomposable, that is, hydrolyzable (hydrolysable) and biodiversity, "born of the moon female formate resin", when it is used for the desired purpose ^, it can be hydrolyzed It can be reused by recycling raw materials. That is, it can be used in the field of recycling such as printing paper containing general resins, etc., and can also be used. It can be recycled without having to be separated from other general papers. In addition, 1 biodegradable resin, the polyurethane resin of the present invention has two SI; shapes: and 2: uot; Known biodegradable tree shovel excellent: Gang = and Yagi right, although it has high strength, but it has the properties of a known product, some high elasticity, high elongation, etc., the towel has health ^

88116687.ptd Page 43 533219 V. Description of the invention (41) Decomposer. Therefore, the polyurethane resin of the present invention may be applied to a field in which the conventional biodegradable resin has insufficient physical properties, regardless of whether the conventional resin has good biodegradability. The present invention also provides a biodegradable tree S. Compared with the conventional biodegradable resins in which the aliphatic diisocyanate is used as a binder, the product can be obtained without a great burden on manufacture, and after decomposition, The diamine produced is not mutagenic, but has safety and environmental adaptability.

88116687.ptd Page 44

Claims (1)

533219 \\ 326 \ 2d- \ 91-02 \ 88116687.ptc Page 48 ^ 3219 VI. Application for patent application f ^^ Year 687 Shown = m ^ t — search for methyl end-fired adducts or copolymers thereof, and formula (1 Q) (10) sz m ig m fij _, the group is an integer of 1 or more) is not aggregated g ^ or two or more kinds of degenerates. ^, A decomposable polyurethane tree in the scope of patent application No. 1 ‘its transformation im2,6 diisocyanatomethylbicyclo [2 · 2 · ι] heptane and / or. The amount of the body used is 0.001 ~ 40wt // fat 7 when the polyol is used as a benchmark; please: = = decomposable polyurethane tree around item 1, Can be used as a polymer film. • As in the first patent application, the resin can be used as a polymer sheet. No. 4 formic acid brewing tree 9. If the decomposable lipid of item i in the scope of patent application, among which 'the resin can be used as a disc box, carbamic acid i purpose tree 1 〇 · As in the scope of patent application No. 1 顼The resin can be used as a polymer: Polyurethane tree 533219 \\ 326 \ 2d- \ 91-02 \ 88116687.ptc Page 50 Invention Patent Specification 533219 88116687.ptc Chinese Degradable Polyurethane Resin Invention Name English DEGRADABLE POLYURETHANE RESIN ♦ Name (Chinese) 1. Ikeda Aya 2. Matsuno Hiroaki 3. Sato Naoki Inventor Name (English) 1. 2. 3. Nationality 1. Japan 2. Japan 3. Japanese residence and residence 1. 300, Shirakawa-cho, Omuta-shi, Fukuoka Prefecture, Japan 2. Tsukiji 919-4, Tamana-shi, Kumamoto Prefecture, Japan 3. 178-4, Shimokawa-machi, Omuta-shi, Fukuoka Prefecture, Japan Name (Name) (Chinese) 1. Mitsui Chemical Co., Ltd. (English) 1. Mitsui Chemical Co., Ltd. Nationality 1. Japanese applicant's residence and residence (office) 1. Saisaka, Chiyoda-ku, Tokyo, Japan Guan 3 Ding Mu 2 Fan No. 5 Representative Name (Chinese) 1. Chinese and Western Hongxing Representative Name (English) 1. Page 1 533219 Case No. 88] lfifiR7 V. Description of the Invention (4) Correction 2 '. 2! : · Page ocnO \ NCO (1 (Formula (1) represents a 2,5-substituted isocyanate or a mixture of the two)) or a 2,6-substituted compound [2 · 2 · 1] heptane and / Or a modified form thereof and a cyanofluorenyl bicyclic ring, a lipid, wherein the polyol is selected from the group consisting of (8): polyurethane polyurethane polyacetate polyol, and (C) sugars Polyol, (B) a mixture of polyhydric alcohols of more than aliphatic type; 20% of the polyhydric alcohol; or a polyhydric alcohol consisting of two kinds of polyhydric alcohols or dihydric alcohols, and A (D) consisting of l · κ, or may be ( D) Polyols that are divided by the condensation of (A) and / or (B) above with alcohols or alcohols, and the above-mentioned moons have no polyols &lt; 2 &gt; as above &lt; 1 &gt; are degradable The polyhydroxycarboxylic acid polyalcohol is given by the formula (2) (2) (In the formula, R1 represents the envy of the linear part, ^ make "π ratio η, the inverse number of 1 to 4 (including the total carbon number of $ 田 ^ ^, Ί / 砹 alkyl group) It is a radical group of 1 to 6, and m is a whole age of 1 or more, shame— 丄 q 甲 ^^^ ^) The aliphatic polyhydroxycarboxylic acid is denatured in the manner that the ancient ☆ carboxyl group becomes a base · &Lt; 3 &gt; As described above &lt; 2 &gt; Decomposable flat ^ 1 soil <♦ amino ester resin, R Φ 彳 (2) is a fluorenyl group having a carbon number of 1 ， 七古 μ *, said u yue yuezhong "Hai .. ™ # &gt;, 儿 τ 丞, or the linear part of the carbon number is 1 and substituted with fluorenyl, ethyl, or propyl extension. Soil &lt; W-base, or the carbon number of the linear part is 533219 Case No. 88Π6687 Λ_ Said amendment 92202. 21 Replace page V. Description of the invention (5) 2 and substituted alkylene group with fluorenyl or ethyl group, or A straight-chain part having 3 carbon atoms and an alkylene group substituted with a fluorenyl group, and formula (2) is an aliphatic polyhydroxycarboxylic acid polyol composed of structural units having the same or two or more types of R1; &lt; 4 &gt; as above &lt; 1 &gt; decomposable Polyurethane resin, in which the aliphatic polyester polyol is selected from the group consisting of formula (3) (3) HO-R2-0Η (where R2 represents a fat having a carbon number of 2 to 2 0 and having a substituent. One or two or more kinds of aliphatic polyalcohols represented by the group (hydrocarbon group) and selected from the formula (4) (4) HOOC-RLCOOH (where R3 represents a possessable substitution having a carbon number of 2 to 20 &Lt; 5 &gt; As described in &lt; 1 &gt;, a degradable polyurethane resin, as described above, &lt; 5 &gt; Wherein the saccharide is one or more compounds selected from the group consisting of monosaccharides or molasses, cellulose or cellulose derivatives; &lt; 6 &gt; as described above &lt; 1 &gt; a degradable polyurethane Resin, in which the aliphatic polyhydric alcohol having a valence of 3 or more is selected from the formula (5) R4 (〇H) n (5) (where R4 represents a hydrocarbon group having 2 to 20 carbon atoms, and η is an integer of 3 to 6) One of two or more compounds shown; &lt; 7 &gt; A degradable polyurethane resin as described above &lt; 1 &gt;, wherein The acid number of the polyol is 1.4 10 mole / g or less persons; &lt; 8 &gt; above &lt; 1 &gt; having the property of decomposing Yue ester polyamine resin, wherein C: \ Master File of Patent Cases \ 88 \ 881] 6687 \ 88] 16687 (Replacement) -2.ptc Page 8 533219 &lt; Jk _ Case No. 88116687 V. Description of the invention (8) The resin made from arsenic acid; &lt; 15 &gt; — a substrate for a disc box, which is divided into the above-mentioned <1> and is a knife% And &lt; 1 6 &gt;-a polymer fiber bundle formed from the above-mentioned <1 &gt; decomposable urethane resin. And; &lt; 17 &gt;-a card base material formed from the decomposable polyacid SI resin of the above &lt; ι &gt;. * A [Best Mode for Carrying Out the Invention] The present invention will be described in detail below. The present invention is a reaction place of 2, 5- / 2, 6-diisocyanatomethyl A [2 · 2 · 1] heptane and / or a modified form thereof with a polyhydric alcohol of the formula (1); ^ = A bicyclic urethane resin, wherein the polyol is one selected from the group consisting of (a) a carboxylic acid polyol, (B) an aliphatic polyester polyol, and (c) a saccharide. A polyol or a mixture of two or more polyols ^ co = ^ a polyol composed of one, or (D) the above-mentioned (A) and / or: aliphatic polyhydric alcohols above the price may be diverged Of polyols. Λ 3 The degradable polyurethane resin of the present invention (hereinafter, sometimes referred to as the "polyurethane resin of the present invention") has hydrolyzability (dehydration with water addition) and biodegradability. That is, the polyurethane resin of the present invention does not only have the degradability of hydrolysis in the presence of acid or alkali, but also has the so-called Biological ^ Solubility. Therefore, the polyurethane resin of the present invention is used in accordance with the intended purpose, for example, the molded product may be discarded or recycled after being hydrolyzed, and it is not polluted even when abandoned in the natural environment. Land loss C: \ General file of patent cases \ 88 \ 88]] 6687 \ 88】 16687 (replacement) -2.ptc page 11 533219 i V. Description of the invention (9) The ball environment has such decomposability, or flexibility. The present invention is related to aliphatic polys, polyhydric or more alcohols, or low polybasic polyalcohols obtained from polyvalent carboxylic acids of these polyhydric carboxylic acids, that is, the present invention ϊϋ1 88116687 Biodegradable poly # &quot; ^ 一 '^ Also has the resin = ester resin. It is not only a polyalcohol that accounts for good strength and elongation of malignant ulcers. It is a group of alcohols selected from alcohols and (C) sugars _A), carboxylic acid polyols, and (B) fat sprays— 7 is a mixture of polyhydric alcohols or copolycondensates. (X) (D) is obtained by combining (A) and / or (B) with the trivalent fat in μ / fan from above. Divided polyols. Among the alcohols, (A) polyhydroxycarboxylic acid polyalcohol refers to an aliphatic polymer and / or polymer whose terminal groups are gradually denatured to become a group. The (A) polyhydroxycarboxylic acid polyol is represented by formula (2) (2) (where 'R1' represents an alkylene group having 1 to 4 carbon atoms in the straight chain portion and an alkylene group having a total carbon number of 1 to 6 including a branched alkyl group, and m is an integer of 1 or more) The oligomer and / or polymer of the aliphatic polyhydroxycarboxylic acid shown has a terminal carboxyl group modified to become a hydroxyl group. For example, a polyhydric alcohol represented by formula (2-1) or formula (2-2) may be mentioned: c: \ General file of patent cases \ 88 \ 88116687 \ _16687 (replace H.ptc, page 12, 533219, case number 88116687, amend 82. 2., 21 Replacement page, V. Description of the invention (11) Butylhexanoic acid, 2-hydroxy -2 -pentylhexanoic acid, 2-hydroxy-2-fluorenylheptanoic acid, 2-hydroxy-2-ethylheptanoic acid, 2-hydroxy-2-propylheptanoic acid, 2-hydroxy-2 -butylheptanoic acid, 2-hydroxy-2-pentylheptanoic acid, 2-hydroxy-2-hexylheptanoic acid, 2-hydroxy-2-fluorenylcaprylic acid, 2-hydroxy-2-ethylcaprylic acid, 2-hydroxy-2-propylcaprylic acid , 2-Hydroxy-2-butyloctanoic acid, 2-Ethyl-2-pentyloctanoic acid, 2-Ethyl-2-hexyloctanoic acid, 2-Ethyl-2-heptyloctanoic acid, 5-Hydroxy-5-propylpropyloctanoic acid, 6-caproic acid, 6-caproheptanoic acid, 6-caprocaprylic acid, 6-capro-6-fluorenylheptanoic acid, 6-capro-6-fluorenylcaprylic acid, 6-capro-6-ethylcaprylic acid, 7- Hydroxyheptanoic acid, 7-hydroxyoctanoic acid, 7-hydroxy-7-fluorenyloctanoic acid, and 8-octanoic acid. Among them, glycolic acid, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 3-hydroxypentanoate Acids and 4-hydroxyvaleric acid are particularly preferred from the viewpoint of producing a biodegradable polyurethane resin having excellent strength. Among them, the resin obtained from hydroxypropionic acid has high strength and forms transparent biodegradability. Hydroxypropionic acid is the most preferred amino acid resin because it has antifungal properties. The aliphatic hydroxycarboxylic acids that can be used in the present invention are not limited by the compounds exemplified above, and they can also be used. One or two or more compounds are used as the raw material of the copolymer. Furthermore, the raw materials of these hydroxycarboxylic acids may also be intramolecular dehydrated cyclic lactones such as 7-hydroxybutyrolactone, or Compounds that form a dehydrated dimerized form such as diethylbenzene and diacetylene, and when the optical isomers are possessed, the ratio of the amount of isomers present is not particularly limited. In the present invention, ( B) Aliphatic polyester polyols refer to those obtained by polycondensation of aliphatic polyols and polyacids. The aliphatic polyols used as raw materials are, for example, formula (3) C .. \ General file of patent cases \ 88 \ 88]] 6687 \ 881] 6687 (Replacement> -2.ptc Page 14 533219 Case No. 88116687 Rev. m. 2 = s .: Replacement page V. Description of the invention (14) For the polyhydric alcohol used in the present invention, the types and amounts of the functional groups of the polyhydric alcohols (A) to (C) described above may also be used. That is, the functional groups and other functional groups may also be used. Polyols that are denatured by reaction with hydroxy compounds, carboxylic acids, amines, etc. For example, for aliphatic polyhydroxycarboxylic acids or aliphatic polyesters, the hydroxyl or carboxyl groups at the end of the polymer chain may be made in advance with the polyol Reaction with polybasic acids, polyacids, or polyamines so that the polymer chain terminal has only hydroxyl groups. Furthermore, it can also react with compounds having functional groups other than hydroxyl groups as needed. In addition, when sugars are used You can also mix or react sugars with other polyols to form polyols that are different from the original polyols, for example, you can also react or mix molasses with other ® polyols to form molasses polyols. When the polyol is (A) an aliphatic polyhydroxycarboxylic acid polyol, it is preferred that the hydroxycarboxylic acid or the polyhydroxycarboxylic acid is selected from the polyhydric alcohols, and the aliphatic polyester shown in (B) is polyvalent. Alcohol and one or more compounds of a group consisting of sugars are reacted so that the terminal group becomes substantially a hydroxyl group. Furthermore, the polyhydric alcohol is (B) a polymer of an aliphatic polyalcohol and an aliphatic polybasic acid. In the case of the oligomer and / or polymer of the aliphatic polyester polyol obtained by the condensation, it is preferable to adjust the aliphatic polyol and the aliphatic polyhydric so that the terminal group can substantially become a hydroxyl group during the polymerization. The raw materials of acids are mol ratios. Here, the so-called π polyol which substantially becomes a hydroxyl group at the terminal group means that the polyol has sufficient hydroxyl groups, which is sufficient to form a polyurethane S resin in its reaction with NBDI. In other words, it is preferable that the acid value determined by the neutralization titration method with a sodium methanol titration solution is 10-4 mol / g or less, and 6 X 10-5 mol / g C: \ Master File of Patent Cases \ 88 \ 88116687 \ 88116687 (Replacement) -2.ptc Page 17 533219 Replacement Page V. Description of the invention (15) The following is better. Furthermore, in the case where the base number of ^ ^ is preferably 1 s, the average hydroxyl value contained in one molecule of the polyhydric alcohol is better, "2 &quot; ^ 上 = 的 其If it is h8 or more, and when the number of hydroxyl groups at the chain end of the compound of formula ") is 1.9, it can also be opened by a polyhydric alcohol with a trivalent or higher valence (5) shown by R4 (〇H) n. The reaction of fatty polyhydric alcohols has a linear structure of aliphatic polyhydric alcohols. Combination of integers of lipids with a valence of 3 or more as shown in formula (5) = / of which 1 ^ is a hydroxyl group having 1 to 2 carbon atoms and η is 3 to 6 Specifically, fat :: one or two or more kinds By. With aliphatic polyacids ^ = hydroxycarboxylic acid polyalcohols or will be made from aliphatic polyalcohols, or at :: ίί :: = polyhydric alcohols are polycondensed to trimethylolpropane and tripotassium to make them with glycerol Alcohols, isopentaerythritols, triols,], 2,6 ~ 3,3-heptyl heptyl, i, 2,4-butan have a bifurcated structure. And temples can be obtained through the cooperation of health, and can be obtained with the "Guang π &quot; polyol ..." polyol can also be chain +-or from low molecular weight to high molecular weight ^ ^ day as the amount of low molecular weight such as' also can The molecular weight was adjusted by subjecting the polyacrylic acid to a polyacrylic acid. For example, the molecular weight can be quantified. Furthermore, the aliphatic polyacetate can be further polymerized to form a low-molecular-weight oligomer and the molecular weight of the polyhydric alcohol used for the decomposition of cellulose has been changed. Therefore, it is not particularly affected. Restriction = It is used for various purposes ___ However, the number-average numerator C is usually used: C: \ Patent Case Total File \ 88 \ Amount] 6687 \ 敝] 6687 (Replace) 2.pic ^^ Page 533219 92, 2. 21 Case No. 88116687_Year Month Revision_ Substantia Gas V. Description of the Invention (16) 'Polyols in an amount ranging from 200 to 100,000. As for polysaccharides, a higher molecular weight is sometimes used. In order to obtain a biodegradable polyurethane resin 'aliphatic polyhydroxycarboxylic acid polyol and aliphatic polyester polyol having a higher strength, the molecular weight range of the aliphatic polyhydroxycarboxylic acid polyol and the aliphatic polyester polyol is preferably 50. 0 to 1 0 0, 0 0 0, preferably 1 '00 to 50, 000. Furthermore, it is more preferably 5,000 to 40,000. If the number-average molecular weight exceeds 1 0, 0 0 0, the amount of NBDI related to the reaction becomes extremely small, and sometimes the use effect of NBDI becomes small. The polyisocyanate compound according to the present invention is of formula (1) ⑴ 6 is a substitution, and the change is (6) (the formula (1) represents a 2,5-substituted compound of isocyanatofluorenyl group, a 2, compound or a mixture of both) and / or a modification thereof body The sex body is, for example, in formula (6) The isocyanurate of NBDI or its block copolymer shown in Formula (7) &quot; OCN NCO (7) 533219 Monochloromethane to obtain polyhydroxy acidic polyester diols. 5 · 3 g. The yield was 100.2. The weight-average molecular weight obtained by GPC of the obtained polypropionic acid-denatured polyester diol (a) was about 3,000, the acid value was 1 17 × 10-5 mol / g, and the warp value was丨 · 92 X⑽3 Mol / g. The amount of butanediol was changed to 0.060 mol, 0.030 mol, and 0.15 mol, and the ratio of the amount of DMC and / 3 to pyridine used was based on the used butanediol. It remained unchanged to prepare three polyhydroxypropionic acid-denatured polyester diols having a weight average molecular weight of about 5,000 (polyester diol (b)), and 0.001 (polyester diol ( c)), and 20,000 (polyesterdiol ㈠)). The acid values of the obtained poly (hydroxypropionic acid) modified polyester diols were 1. 4 2 X 1 0-5 mol / g, 1. 3 3 X 1 mol / g, 1. 14χ 105 mol / g, respectively. Gram, and its hydroxyl value was 丨 · 2ΐχ mol / g, 6.02χ 10-4 mol / g, and 2.99χ mol_4 / mo. 、 Synthesis Example 2 Synthesis of chloropropionic acid modified poly 1 polyol (e) ~ (h) Under the condition that the gas is used for flushing, a five-necked flask (1 liter) equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube is implemented. Weight average molecular s is about 3,000 and a number average molecular weight, a polyhydroxypropionic acid oligomer of i, 〇, 〇g (hydroxyl 0. ^ 086 2 mole) and dichloromethane 3 0 0g to dissolve the former, followed by gasification of 2-chloro-1,3-dimethylimidazole tablets (hereinafter referred to as 0 red) 17.48 (0.103 mole), 5.59g of ethylene glycol and isoprene Alcohol 0.9 g (molar ratio of ethylene glycol to isoprene tetraol is 9:67; total 0.0967 mole) was charged therein, and 24.12 g of / 5-methylpyridine (0.259 mole) was added. And then stirred at 30 ~ 4 ° C for 3 hours to carry out the reaction. After the reaction was completed, a 30% hydrochloric acid aqueous solution was used. ^, Patent Archives, 88, 88] 6687, 88]] 6687 ^^. 2. ^ Fourth 533219 ^ _ Case No. 88116687_ Year Month Day Amendment 9L · 2, —7 Schematic Illustration \\ 326 \ 2d- \ 91-02 \ 88116687.ptc Page 45