JP2001081152A - Polyurethane resin having decomposing property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane resin having decomposing property, namely hydrolyzable property and biodegradability by reacting a specific polyol with diisocyanatomethylbicycloheptane. SOLUTION: This polyurethane resin is obtained by reacting, e.g. (A) a polyol comprising a mixture or copolycondensation polymer selected from (i) polyhydroxycarboxylic acid polyol of formula I (R1 is a 1-4C alkylene; m>=1), (ii) a fatty acid polyesterpolyol and (iii) saccarides or (iv) a polyol which may be branched by condensing a component (i) and/or (ii) with a tri- or more valent aliphatic polyvalent alcohol with (B) 2,5/2,6- diisocyanatomethylbicyclo[2.2.1]heptane of formula II and/or its modifier. It is preferable that the component B is 0.001-40 wt.% based on the component A in the above resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to 2,5- / 2,6
A novel polyurethane resin having a specific structure using diisocyanatomethylbicyclo [2.2.1] heptane and / or a modified form thereof as a binder, more specifically degradable, that is, hydrolyzable and biodegradable The present invention relates to a novel polyurethane resin having properties and a molded product obtained by molding the same.

[0002]

2. Description of the Related Art In recent years, environmental pollution by plastic waste has become a worldwide problem. The biggest sources of this problem are polystyrene, vinyl chloride,
Since plastics such as polypropylene do not have biodegradability, they may remain in the soil even if they are landfilled. In addition, even when incinerated, plastics generally have a large heat of combustion and cause air pollution by combustion gas, and therefore, it is difficult to cope with only ordinary incineration equipment. In addition, although recycling is gradually becoming widespread, a significant portion of plastic applications are unsuitable for recycling in the first place. Under such circumstances, biodegradable plastics that can be decomposed in a natural environment are being developed. Many biodegradable resins are already known, typically polyglycolic acid and polylactic acid,
Polyhydroxybutyric acid, polyhydroxyvaleric acid, polyhydroxycarboxylic acids such as polycaprolactone, and polybutylene succinate obtained by polymerizing polyhydric alcohols and polybasic acids, and aliphatic polyesters such as polybutylene adipate are often used. Are known. Also, polyamino acids such as polysuccinimide, molasses, cellulose and modified cellulose, saccharides such as chitin and chitosan and modified products thereof, resins derived from modified proteins such as gelatin, sericin, and lignin, or vegetable oils Utilization of natural macromolecules and the like derived from the same is being studied. However,
The biodegradable resins are still insufficient as alternatives to conventional resins in physical, mechanical, or chemical properties for many applications where conventional resins are used. In particular, polylactic acid is the only biodegradable resin that is colorless and transparent, and has excellent tensile strength, but has poor elasticity and elongation and is brittle. In addition, since there are many products that place a large load on manufacturing, various devices have been devised.

One of the methods is to react an aliphatic polyester oligomer with a polyisocyanate compound. For example, a method of reacting polylactide and polyisocyanate to obtain an aliphatic polyester is disclosed in JP-A-5-148352. Examples of the use of a polyisocyanate compound as a binder for an aliphatic polyester comprising a polyhydric alcohol and a polybasic acid are disclosed in JP-A-4-189822 and JP-A-6-157703, and Examples of bonding saccharides with polyvalent isocyanates are disclosed in
It is disclosed in, for example, Japanese Patent No. 302061. However, the polyisocyanate compounds used there are generally highly harmful, and the diamines generated when decomposed have a large load on the natural environment. Therefore, examples using hexamethylene diisocyanate and isophorone diisocyanate, which are aliphatic isocyanates with a small load on the natural environment, are disclosed in JP-A-5-70543 and JP-A-5-70575. However, when hexamethylene diisocyanate is used, the operability of the production is poor due to the high vapor pressure, or a biodegradable resin having excellent tensile elongation is obtained, but the mechanical properties such as yield strength and breaking strength are inferior. Had disadvantages. On the other hand, when isophorone diisocyanate is used, there is a problem that the reaction rate is extremely slow due to the different reactivity of the two isocyanate groups, and a heavy load is imposed on the production.

[0004]

In view of the problems of the prior art, an object of the present invention is to provide a novel resin having improved physical properties as compared to conventional biodegradable resins and having degradability.
Provide a resin that is safer than conventional technology when released into the natural environment, has a smaller load during reaction, and has degradability, that is, a hydrolyzable and biodegradable resin, and a molded article thereof. It is to be.

[0005]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the corresponding diamine is 2,5- /
2,6-diisocyanatomethylbicyclo [2.2.1]
Surprisingly, polyurethane resins using heptane (hereinafter abbreviated as NBDI) as a polymer binder for degradable resins maintain or improve the strength of known biodegradable resins, and at the same time improve elongation and elasticity. Further, they have found that a polyurethane resin having a decomposable property can be obtained with less burden on production, and the present invention has been completed.

That is, the present invention relates to (1) a polyol and a compound represented by the formula (1)

Embedded image (Formula (1) represents a single or a mixture of a 2,5-substituted and a 2,6-substituted isocyanatomethyl group, respectively) 2,5- / 2,6-diisocyanatomethyl A polyurethane resin obtained by reacting bicyclo [2.2.1] heptane and / or a modified product thereof, wherein the polyol is (A) a polyhydroxycarboxylic acid polyol, (B) an aliphatic resin, One or a mixture of two or more selected from the group consisting of polyester polyols and (C) saccharides, or a polyol composed of a co-condensed polymer, or (D) (A) and / or (B) is trivalent or more Degradable polyurethane resin which is a polyol which may be branched by condensation with an aliphatic polyhydric alcohol,

(2) In the above (1), (A) the polyhydroxycarboxylic acid polyol has the formula (2)

Embedded image (In the formula, R ¹ is an alkylene group having 1 to 4 carbon atoms in the straight chain portion, and represents an alkylene group having 1 to 6 carbon atoms including a branched alkyl group, and m is 1 or more. A degradable polyurethane resin obtained by modifying a terminal carboxyl group of an aliphatic polyhydroxycarboxylic acid represented by the formula

(3) In the above (2), R ¹ in the formula (2) represents an alkylene group having 1 carbon atom, a methyl group, an ethyl group, or a propyl group having 1 carbon atom in a straight chain portion. An alkylene group substituted by any one of which has a carbon number of 2
Wherein an alkylene group substituted with a methyl group or an ethyl group, or an alkylene group having 3 straight-chain portions and substituted with a methyl group, wherein R ¹ is the same or 2 Degradable polyurethane resin which is an aliphatic polyhydroxycarboxylic acid polyol comprising at least one kind of structural unit,

(4) In the above (1), the aliphatic polyester polyol is represented by the formula (3)

Embedded image (Wherein, R ² represents an optionally substituted aliphatic hydrocarbon group having 2 to 20 carbon atoms), and one or more selected from aliphatic polyhydric alcohols represented by the formula ( 4)

Embedded image (Wherein R ³ represents an optionally substituted aliphatic hydrocarbon group having 2 to 20 carbon atoms) by reacting with one or more kinds selected from aliphatic polybasic acids represented by the formula: A decomposable polyurethane resin that is obtained;

(5) In the above (1), the decomposable polyurethane resin, wherein the saccharide is one or more compounds selected from monosaccharides, molasses, cellulose and cellulose derivatives,

(6) In the above (1), the trihydric or higher aliphatic polyhydric alcohol is represented by the formula (5)

Embedded image (Wherein, R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms;
n is an integer of 3 to 6. A) a decomposable polyurethane resin which is one or more selected from compounds represented by

(7) The polyurethane resin according to (1), wherein the polyol has an acid value of 10 ^-4 mol / g or less,

(8) In the above (1), 2,5- /
2,6-diisocyanatomethylbicyclo [2.2.1]
The modified heptane is represented by the formula (6)

Embedded image An isocyanurate of 2,5- and / or 2,6-diisocyanatomethylbicyclo [2.2.1] heptane represented by the formula:

Embedded image A uretdione form of 2,5- and / or 2,6-diisocyanatomethylbicyclo [2.2.1] heptane represented by the following formula, or a block form thereof;

Embedded image A buret form of 2,5- and / or 2,6-diisocyanatomethylbicyclo [2.2.1] heptane represented by the following formula, or a block form thereof, formula (9)

Embedded image A trimethylolpropane adduct or a block thereof represented by the formula:

Embedded image (Wherein, Z is an integer of 1 or more) One or more decomposable polyurethane resins selected from the group consisting of polycarbodiimides represented by the formula:

(9) In the above (1), 2,5- /
2,6-diisocyanatomethylbicyclo [2.2.1]
A decomposable polyurethane resin in which the amount of heptane and / or a modified product thereof is 0.001 to 40% by weight based on the polyol;

(10) The hydrolyzable polyurethane resin of (1) to (9),

(11) The biodegradable polyurethane resin of the above (1) to (9),

(12) A composition comprising the polyol described in (1) and 2,5- / 2,6-diisocyanatomethylbicyclo [2.2.1] heptane and / or a modified product thereof. Polyurethane resin raw material composition having a decomposable characteristic,

(13) A polymer film formed by molding the decomposable polyurethane resin of the above (1),

(14) A polymer sheet formed by molding the decomposable polyurethane resin of the above (1),

(15) A disk case base obtained by molding the decomposable polyurethane resin of the above (1),

(16) A polymer staple formed by molding the decomposable polyurethane resin of the above (1), and

(17) A card base obtained by molding the decomposable polyurethane resin of the above (1).

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention relates to 2,5- / 2,6-diisocyanatomethylbicyclo [2.2.1] heptane of the formula (1) and / or a modified product thereof, and (A) a polyhydroxycarboxylic acid polyol, (B) a polyol selected from the group consisting of aliphatic polyester polyols and (C) saccharides, or a mixture of two or more kinds or a cocondensation polymer, or (D) (A) and / or (B), It is a decomposable polyurethane resin obtained by reacting with a polyol which may be branched by condensing with a trihydric or higher aliphatic polyhydric alcohol.

The decomposable polyurethane resin of the present invention (hereinafter sometimes referred to simply as the polyurethane resin of the present invention) has hydrolyzability and biodegradability. That is, the polyurethane resin of the present invention has so-called biodegradability, which is not only degradable in the presence of an acid or alkali, but also hydrolyzed by a microbial hydrolase in a natural environment. Therefore, the polyurethane resin of the present invention may be used for a desired purpose, for example, after being used as a molded article, hydrolyzed to be discarded or recycled, or may be abandoned to the natural environment, for example. A biodegradable polyurethane resin that does not impair the global environment. Not only has such degradability, but also has good strength, elongation and elasticity as a resin.

The polyol according to the present invention may be one or a mixture of two or more selected from the group consisting of (A) a polyhydroxycarboxylic acid polyol, (B) an aliphatic polyester polyol and (C) a saccharide, or a co-degenerate. It is a polyol consisting of a union, or a polyol which may be branched by condensing (D) (A) and / or (B) with a trihydric or higher aliphatic polyhydric alcohol. In these polyols, the (A) polyhydroxycarboxylic acid polyol is an oligomer and / or a polymer obtained from an aliphatic hydroxycarboxylic acid, and refers to a polyol having a carboxyl group terminal modified with a hydroxy group.

[0026] That is, the (A) polyhydro according to the present invention
The xycarboxylic acid polyol has the formula (2)

Embedded image (In the formula, R ¹ is an alkylene group having 1 to 4 carbon atoms in the straight chain portion, and represents an alkylene group having 1 to 6 carbon atoms including a branched alkyl group, and m is 1 or more. Which is an integer of a) and an oligomer and / or a polymer of an aliphatic hydroxycarboxylic acid represented by the formula (1), wherein the terminal carboxyl group is modified to a hydroxy group. For example, those represented by the formula (2-1) or the formula (2-2) can be mentioned.

Embedded image

Embedded image (In these formulas, R ¹ represents an alkylene group having 1 to 4 carbon atoms in the straight-chain portion, and an alkylene group having 1 to 6 carbon atoms in total, including a branched alkyl group;
² represents an optionally substituted aliphatic hydrocarbon group having 2 to 20 carbon atoms, and a and b are integers of 1 or more).

Equations (2), (2-1) and (2-2)
In the formula, R ¹ is, specifically, an alkylene group having 1 carbon atom; a methyl group having 1 carbon atom in a straight-chain portion,
An alkylene group substituted with any of an ethyl group or a propyl group; an alkylene group substituted with a straight-chain portion having 2 carbon atoms and a methyl group or an ethyl group; or a straight-chain portion having 3 carbon atoms; A methyl group-substituted alkylene group. In these formulas, even if R ¹ is one type, when m in the formula is 2 or more, it is a copolymer containing two or more types of structural units. Is also good.

The aliphatic hydroxycarboxylic acid which is a raw material of the aliphatic polyhydroxycarboxylic acid oligomer or polymer represented by the formula (2) is specifically, for example, glycolic acid, lactic acid, 2-hydroxybutyric acid, -Hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyvaleric acid, 3
-Hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxy-2-methylbutyric acid, 2
-Hydroxy-2-ethylbutyric 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-butylhexanoic acid, 2-hydroxy-2-pentylhexanoic acid, 2-hydroxy-2-methylheptanoic 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-methyloctanoic acid,
2-hydroxy-2-ethyloctanoic acid, 2-hydroxy-2-propyloctanoic acid, 2-hydroxy-2-butyloctanoic acid, 2-hydroxy-2-pentyloctanoic acid, 2-hydroxy-2-hexyloctanoic acid, 2-
Hydroxy-2-heptyloctanoic acid, 5-hydroxy-5-propyloctanoic acid, 6-hydroxycaproic acid, 6-hydroxyheptanoic acid, 6-hydroxyoctanoic acid, 6-hydroxy-6-methylheptanoic acid, 6-hydroxy- 6-methyloctanoic acid, 6-hydroxy-6
-Ethyloctanoic acid, 7-hydroxyheptanoic acid, 7-
Examples include hydroxyoctanoic acid, 7-hydroxy-7-methyloctanoic acid, and 8-hydroxyoctanoic acid.

Of these, glycolic acid, lactic acid,
-Hydroxybutyric acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, and 4-hydroxyvaleric acid are preferable in terms of giving a biodegradable polyurethane resin having particularly excellent strength. It is most preferable because it forms a transparent biodegradable polyurethane resin and further has advantages such as mold resistance. The aliphatic hydroxycarboxylic acids that can be used in the present invention are not limited to the above exemplified compounds, and one or two of these compounds may be used.
More than one species can be used as a raw material for the copolymer. In addition, the raw materials of these hydroxycarboxylic acids may be in the form of intramolecularly dehydrated and cyclized lactones such as γ-butyrolactone or dehydrated and dimerized forms such as glycolide and lactide, and have optical isomers. The abundance ratio is not particularly limited.

In the present invention, the aliphatic polyester polyol (B) is obtained by polycondensing an aliphatic polyhydric alcohol and a polybasic acid. The aliphatic polyhydric alcohol as a raw material is, for example, a compound represented by the formula (3)

Embedded image Are glycols represented by In the formula (3), R ² represents an optionally substituted aliphatic hydrocarbon group having 2 to 20 carbon atoms, and specific examples of the glycol represented by the formula (3) include ethylene glycol, Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-
Nonanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol and the like can be mentioned. One or more of these can be used. Among these, ethylene glycol, 1,4-
Butanediol and 1,4-cyclohexanedimethanol are preferred. However, the material is not limited to these exemplified compounds, and is not particularly limited as long as it is a raw material capable of forming an aliphatic polyester. Further, other polyhydric alcohols may be used.

The raw material aliphatic polybasic acids are represented by the formula (4)

Embedded image Are aliphatic polybasic acids represented by In the formula (4), R ³
Represents an optionally substituted aliphatic hydrocarbon group having 2 to 20 carbon atoms. Specific examples of the aliphatic polybasic acid represented by the formula (4) include oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and undecane Examples thereof include diacid, dodecanedioic acid, maleic acid, and fumaric acid. One or more of these may be used, and the form may be an acid anhydride or an ester. The acid component capable of forming an aliphatic polyester is not limited to these exemplified compounds. It is not particularly limited as long as it is a raw material.

As the aliphatic polyester polyol (B), polyethylene succinate, polybutylene succinate, polyethylene adipate, polybutylene adipate, and the like can be used from the viewpoint of the price and availability of the raw material and the flexibility of the obtained resin. Examples include polyethylene succinate adipate and polybutylene succinate adipate, but are not particularly limited.

The (C) saccharide according to the present invention includes monosaccharides, disaccharides, oligosaccharides, polysaccharides, and / or derivatives thereof,
Refers to denatured, for example, specific examples of monosaccharides, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose,
Talose, fructose, glucopyranose, glucofuranose, galactofuranose, arabinopyranose,
Fructopyranose, 2-deoxyribose, xylulose, ribulose, sedoheptulose, rhamnose, fucose, glucosamine, galactosamine and the like. These are one of these compounds regardless of the ratio of optical isomers.
Species or disaccharides or polysaccharides composed of two or more species, enolized forms, oxidized forms, reduced forms, modified forms such as glycosides, or mixtures or molasses thereof Good. The saccharides used in the present invention include, of course, cellulose in which these form a long chain, cellulose nitrate, cellulose acetate, ethyl cellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, cuprammonium rayon, cuprophan, Bemberg, Hemicellulose, starch, gum arabic, guar gum, locust bean gum, acacia gum, chitin, chitosan and the like and modified products thereof are not particularly limited as long as they can be used as a polyol.

As the polyol used in the present invention, those in which the types and amounts of the functional groups of the polyols (A) to (C) are adjusted may be used. That is, those modified by reacting a functional group with another hydroxy compound, carboxylic acid, amino compound or the like may be used. For example, aliphatic polyhydroxycarboxylic acids and aliphatic polyesters are prepared by reacting a hydroxyl group or a carboxyl group at the polymer chain terminal with a polyhydric alcohol or a polybasic acid or a polyamine in advance to substantially polymerize the polymer chain terminal group. It can be a group alone. Moreover, you may make it react with the compound which has another functional group other than a hydroxy group suitably as needed. Furthermore, when a saccharide is used, a new polyol may be obtained by mixing or reacting the saccharide with another polyol. For example, a molasses polyol may be obtained by reacting or mixing molasses and a polyol.

In particular, when the polyol is the aliphatic polyhydroxycarboxylic acid polyol of (A), the hydroxycarboxylic acid or polyhydroxycarboxylic acid is converted to a polyhydric alcohol, an aliphatic polyester polyol represented by (B) and a saccharide. It is desirable to react with one or more members selected from the group so that the terminal group is substantially a hydroxy group. Further, an oligomer of an aliphatic polyester polyol obtained by polycondensing the polyol (B) with the aliphatic polyhydric alcohol and the aliphatic polybasic acid and / or
Alternatively, in the polymer, it is desirable that the raw material molar ratio between the aliphatic polyhydric alcohol and the aliphatic polybasic acid used in the polymerization is adjusted so that the terminal group becomes substantially a hydroxy group.

The term "polyol having a substantially hydroxyl group as a terminal group" means that it has a sufficient number of hydroxyl groups to form a polyurethane resin in the reaction with NBDI, and is preferably sodium methylate. The acid value measured by neutralization titration with a titrant is 10 ⁻⁴ mol /
and that g or less, more preferably 6 × 10 ^{- 5}
mol / g or less. When the hydroxyl value is measured, the average number of hydroxyl groups contained in one molecule in the polyol is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 1.9 or more. Most preferably, it is 2.0 or more.

In adjusting the number of hydroxy groups at the terminal of the polymer chain, the formula (5)

Embedded image The polyol having a linear molecular structure can be made into a branched structure by a reaction with a trihydric or higher aliphatic polyhydric alcohol represented by the following formula. In the trihydric or higher aliphatic polyhydric alcohol represented by the formula (5), R ^{4 in} the formula has 1 to 2 carbon atoms.
It is a compound in which 0 is a hydrocarbon group and n is an integer of 3 to 6, and is one or more kinds. Specifically, when an aliphatic polyhydroxycarboxylic acid polyol or an aliphatic polyester polyol composed of an aliphatic polyhydric alcohol and a polybasic acid is produced by polycondensation, or after the polycondensation, glycerin, pentaerythritol, Methylolpropane, trimethylolethane, trimethylolheptane, 1,2,4-butanetriol, 1,2,6-
A polyol having a branched structure is obtained by condensation with hexanetriol or a saccharide.

The molecular weight of the polyol used in the present invention can also be controlled by reducing the molecular weight of a high molecular weight one or by increasing the molecular weight of a low molecular weight one. For example, polyhydroxycarboxylic acids and other aliphatic polyesters can be further polymerized to obtain a high molecular weight, or high molecular weight celluloses can be decomposed and used as low molecular weight oligomers. The molecular weight of the polyol to be used is not particularly limited since it can be changed in accordance with various uses, but usually a polyol having a number average molecular weight in the range of 200 to 100,000 is used. Polysaccharides of higher molecular weight may be used. In order to obtain a polyurethane resin having higher strength and biodegradability, the molecular weight range of the aliphatic polyhydroxycarboxylic acid polyol and the aliphatic polyester polyol is preferably from 500 to 100,00.
0, more preferably 1,000 to 50,000,
More preferably, it is 5,000 to 40,000. NBD related to the reaction when the number average molecular weight exceeds 100,000
The amount of I may become very small, and the effect of using NBDI may become extremely small.

The polyisocyanate compound according to the present invention has the formula (1)

Embedded image (Formula (1) represents NBDI represented by 2,5-substituted or 2,6-substituted isocyanatomethyl group alone or a mixture thereof) and / or a modified product thereof. Is, for example, the equation (6)

Embedded image The isocyanurate form of NBDI represented by the following formula, or its block form, the formula (7)

Embedded image A uretdione form of NBDI represented by the formula or a block form thereof, formula (8)

Embedded image NBDI bullet represented by the following formula, or its block, formula (9)

Embedded image A trimethylolpropane adduct of NBDI represented by the following formula, or a block thereof, formula (10)

Embedded image (Z is an integer of 1 or more) NBDI polycarbodiimide is preferred from the viewpoint of easy synthesis or availability,
The present invention is not limited to these, and two or more types of NBDI and / or modified products thereof may be used in combination.

In the present invention, the polyol and NB
By reacting with DI, a desired polyurethane resin having decomposability can be obtained, but the method is not particularly limited. The reaction may be carried out in the presence or absence of a solvent, in the presence or absence of a catalyst, and the reaction temperature may be NBDI or a modified product thereof as a raw material or a polyol used in the present invention. Can be adjusted arbitrarily according to the physical properties of the resin or the properties of the obtained polyurethane resin. NBDI for reaction
The amount added is not particularly limited because it can be changed according to the molecular weight of the polyol used in the present invention, the number of terminal functional groups, or desired physical properties, but is usually not limited to the total weight of the raw materials involved in the reaction. 0.001 to 40% by weight, preferably 0.01 to 25% by weight, more preferably 0.01 to 10% by weight, and most preferably 0.01 to 5% by weight. If it exceeds 40% by weight, the properties of conventional polyols may not be sufficiently exhibited, or the degradability may be insufficient. If it is less than 0.001%, the effect of reacting with NBDI may be almost lost.

When a solvent is used, usable solvents include, for example, water, benzene, toluene, xylene, mesitylene, chlorobenzene, o-dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, trichloroethylene. , Tetrachloroethane, tetrachloroethylene, tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, sulfolane And the like, but there is no particular limitation. When a urethanation catalyst is used, specific examples of the catalyst include dibutyltin dilaurate, tetramethylbutanediamine, 1,4-diaza
[2,2,2] bicyclooctane, tin octoate, 4-
Methylmorpholine, triethylamine and the like can be used, but are not particularly limited. The amount of the urethanization catalyst may be used according to a known urethanation reaction, and is not particularly limited.

In the present invention, the reaction temperature is not particularly limited because it depends on the type of the polyol to be used and the type of the polyurethane resin to be produced. The reaction takes place in the temperature range. In the presence of a solvent, the reaction is usually carried out in the range from room temperature to the boiling point of the solvent. In the present invention, after a polyol and NBDI are reacted to prepare a prepolymer having a polymer chain terminal having an isocyanate group substantially, the reaction is further carried out to obtain a decomposable polyurethane resin. For example, a linear aliphatic polyester polyol is reacted with NBDI to form a urethane foam in the presence of water or a biodegradable polycarbodiimide in the presence of a carbodiimidization catalyst after substantially converting the isocyanate group ends. You can also. A foamed polyurethane having degradability or biodegradability by forming a foam can be obtained.

The polyurethane resin of the present invention obtained as described above may have, for example, a urea bond, an amide bond, a carbodiimide bond, an allophanate bond, a burette bond, in addition to the urethane bond formed by the reaction between the polyol and NBDI. The resin structure may have an isocyanurate bond, a uretonimine bond, an imide bond, or the like, but is not particularly limited. The presence of these bonds can be arbitrarily selected depending on the type of NBDI and / or its modified product to be used, the type of functional group of the polyol, the reaction conditions, and the like. For example, in order to obtain a degradable and biodegradable polyurethane resin having an isocyanurate bond, an isocyanurate form of NBDI is used as a raw material, or a polyol and NBDI are reacted in advance to form a terminal functional group with isocyanurate. By decomposing and then reacting in the presence of an isocyanurate-forming catalyst, a degradable and biodegradable polyurethane resin having an isocyanurate bond can be obtained.
In particular, in the present invention, the resulting degradable polyurethane resin, as a biodegradable resin, has a hardness not available in conventional biodegradable resins, but at the same time has excellent elasticity and flexibility. In addition, in a specific bonding mode such as a carbodiimide bond or an imide bond, heat resistance and chemical resistance are imparted, so that a new use as a degradable and biodegradable resin can be developed.

The decomposability, which is an excellent performance of the polyurethane resin of the present invention, is that it is hydrolyzed by an acid or alkali aqueous solution,
It refers to a phenomenon that becomes soluble in water, for example, usually, a powdered resin is usually in an alkaline aqueous solution having a sufficient amount of an alkaline component, at a temperature in the range of room temperature to 100 ° C, within 72 hours, preferably Within 24 hours, more preferably within 5 hours. The sufficient amount of the alkali component is usually at least the number of moles of the number of structural units of the resin. The term "biodegradable" refers to a phenomenon of being hydrolyzed in a natural environment by the catalytic action of a microbial hydrolase and decomposed into water and carbon dioxide. Further, in the present invention, the reaction of NBDI and / or a modified product thereof is much faster than that of isophorone diisocyanate, and the operation load required for the production is small, which is industrially excellent as a polyurethane resin. .

The polyurethane resin of the present invention, as a biodegradable resin, is tough and has elasticity and flexibility at the same time, so that it can be used for various applications. Accordingly, the polyurethane resin of the present invention can be used in addition to uses obtained by general processing as a polymer film, a polymer sheet, a tube, a foam, and a fiber, for example, a short fiber, a long fiber, a nonwoven fabric, a porous substrate, and a bowel bag. , Garbage bags, sandbags, thermal insulation cases, food trays, wrap films, chopsticks, spoons, forks, cups, sponges, bottles, water-absorbent sheets, moisturizing sheets, agricultural mulching films, disk case bases, polymer staples, card bases , Blister packs, filters for cigarette smoke, coating agents such as paper, laminating, rods for blocking lacrimal passages, paper strength agents, microcapsules for thermal paper and pressure-sensitive paper, microcapsules for pharmaceuticals, sustained-release preparations, fertilizers and soil improvement Drug microcapsules, sutures, suture clips, syringes, disposable clothing, surgical instruments, Semi-permeable membrane, support or osteosynthesis for treatment of fractures, etc., transplantation equipment or graft, fishing line, fish net, artificial bait, urn, nail polisher, bath pumice, gardening equipment, deodorant microcapsules or containers and packaging ,
Air freshener microcapsules or containers and packaging, shrink films for labels, adhesives, hot melt adhesives, recovered paper storage containers, packing bands, adhesive tapes, cushioning materials, coin packaging films, coating masking films, eyeglass frames, etc. Can be used for The polyurethane resin of the present invention can be widely applied to such uses by taking advantage of its degradability, particularly its biodegradability and excellent physical properties as a resin.

In the present invention, in particular, a biodegradable polyurethane resin obtained by the reaction of an aliphatic hydroxycarboxylic acid and NBDI is used as a packaging material for a polymer film, a polymer sheet, a disk case base or the like due to its toughness and transparency. Excellent as material and card base material.
Further, the polyurethane resin of the present invention is suitable for use as a decorative fiber or a nonwoven fabric because of its flexible texture when formed into fibers.

In producing a molded product such as a polymer film, a polymer sheet, a substrate for a disk case or a card substrate, the method includes, for example, a solution casting method and a calendering method. When the solution casting method is used, for example, chloroform, methylene chloride, benzene, acetonitrile, acetone, toluene, xylene, N, N-dimethylformamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidone,
After a solution is formed using 3-dimethyl-2-imidazolidinone or the like, the solution is cast on a smooth surface and the solvent is removed, but the solvent used is not particularly limited.

In the case of melt extrusion molding,
Known T-die method, inflation method and the like are applied.
The extrusion temperature is not particularly limited because the melting temperature varies depending on the type of resin to be produced, but is usually 100 to 280.
Temperature range. If the molding temperature is low, it is difficult to obtain molding stability, and it is easy to fall into overload. Conversely, if the molding temperature is high, the polymer may be decomposed, which may cause a decrease in the molecular weight, a decrease in the strength, and a coloring.

The polymer film, polymer sheet and the like according to the present invention may be unstretched or stretched, but have stiffness, moldability, mechanical strength, hardness, impact strength, dimensional stability and bending resistance. It is preferable to uniaxially or biaxially stretch the obtained film or sheet in order to improve the properties. In the case of uniaxial stretching, it is usually stretched 1.1 to 5 times in the machine direction or the transverse direction. In the case of biaxial stretching, uniaxial stretching and biaxial stretching may be performed sequentially or simultaneously. The stretching temperature is not particularly limited because it varies depending on the structure and configuration of the polyurethane resin to be used.
The range of (glass transition temperature) to (Tg + 50 ° C.) is preferable. If the temperature is higher than this temperature range, the strength may not be improved by stretching in some cases. After molding, the obtained molded article may be subjected to a heat treatment at a temperature of Tg or more and less than the melting point. The heat treatment time is usually 1 second to 30 minutes.

In the present invention, when the obtained polyurethane resin is processed as a molded product, it may be a mixture or a composite with another resin, and may be a light stabilizer, a plasticizer,
Additives such as an antioxidant, a heat stabilizer, a filler, a coloring inhibitor, and a pigment may be used to further improve physical properties.

As described above, the polyurethane resin of the present invention and its molded product are obtained. Since the molded product has hydrolyzability, after being used for a desired purpose, it is hydrolyzed in an aqueous acid or alkali solution or biodegraded by the action of microorganisms in a natural environment. The biodegradable resin referred to in the present invention mainly refers to a resin that can be composted.
Refers to a resin whose degree of decomposition calculated from the amount of generated carbon dioxide is 60% or more in 3 months in a biodegradability test based on / CD14855. It is generally said that a resin that does not reach a degree of decomposition of 60% or more in three months has poor biodegradability, and may cause inconvenience when disposed of in compost or when released to nature.

The decomposable polyurethane resin raw material composition of the present invention comprises the polyol (1) and NBD
It is a composition containing I and / or its modified product, and can be made into the polyurethane resin of the present invention by increasing the temperature or adding a compound such as a catalyst that initiates the reaction. This composition is prepared according to (A) to (1) above.
With respect to 100 parts by weight of the polyol shown in (D), NB
0.001 to 70 parts by weight of DI and / or a modified product thereof,
Preferably 0.01 to 30 parts by weight, more preferably,
Containing 0.01 to 10 parts by weight of an aliphatic polyhydric alcohol, preferably a biodegradable polyhydric alcohol.
To 1000 parts by weight, preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight. Further, it may contain additives such as a catalyst, a foaming agent such as water or an inert gas, a light stabilizer, a plasticizer, an antioxidant, a heat stabilizer, a filler, a coloring inhibitor, and a pigment. If the amount of NBDI and / or its modified product is less than 0.001 part by weight, the reaction for generating a urethane bond may be insufficient. Here, the aliphatic polyhydric alcohols refer to those exemplified above, and may or may not be contained in the decomposable polyurethane resin raw material composition. If it exceeds, aliphatic polyhydric alcohols having biodegradability are preferred.

EXAMPLES The present invention will be more specifically described below with reference to Examples and Comparative Examples.
I will tell. The present invention is limited to these examples.
There is no.Hydroxyl value  The hydroxyl value shown in Synthesis Examples and Examples is based on JIS K00
Measured by the method according to No. 70, and the unit of the hydroxyl value is m
ol / g.Weight average molecular weight  Weight average molecular weight, depending on the type and molecular weight of the polymer,
It was measured by GPC in a chloroform solvent.Acid value and number average molecular weight  The acid value and the number average molecular weight of the polyhydroxycarboxylic acid are
In a solution of methylene chloride / methanol = 7/3 (volume ratio)
With N / 100-sodium methylate / methanol solution
By making the liquid a titrant and titrating with an automatic titrator,
The terminal carboxyl arithmetic was calculated and determined.

Synthesis Example 1Polylactic acid-modified polyester polyols (a) to (d)
Synthesis  One tank equipped with a stirrer, thermometer, cooling tube, and nitrogen inlet
After purging the 5-neck flask with nitrogen, self-dehydration
The weight-average molecular weight of which is increased by condensation to about 3,000
0, polylactic acid oligomer having a number average molecular weight of 1,160
100.0 g (0.0862 mol of carboxyl groups) and
Add 300 g of methylene chloride to dissolve, then add 2-chloro
B-1,3-dimethylimidazolidinium chloride
(Hereinafter abbreviated as DMC) 17.48 g (0.103
Mol), 9.01 g (0.10 g) of 1,4-butanediol
Moles) and 24.12 g of β-picoline (0.25
9 mol) and stirred at 30 to 40 ° C. for 3 hours.
went. After completion of the reaction, the reaction solution was added with a 30% hydrochloric acid aqueous solution and
Washed sequentially with water. Then, dichloromethane was removed under reduced pressure.
Polylactic acid-modified polyester diol 10
5.3 g were obtained. The yield was 100%. Obtained
GPC of polylactic acid-modified polyester diol (a)
The obtained weight average molecular weight is about 3,000, and the acid value is
1.17 × 10^{− 5}mol / g, hydroxyl value 1.92 ×
10^-3mol / g. 1,4-butanediol
Of 0.060 mol, 0.030 mol, 0.01
5 moles, DM for butanediol used
C and β-picoline are used in the same amount,
The amount is about 5,000 (polyester polyol (b)),
10,000 (polyester polyol (c)), 2
3,000 (polyester polyol (c))
A polylactic acid-modified polyester diol was prepared. Obtained
The acid value of the polylactic acid-modified polyester diol
1.42 × 10^-5mol / g, 1.33 × 10
^-5mol / g, 1.14 × 10 −5 mol / g
And the hydroxyl value is 1.21 × 10^-3mol
/ G, 6.02 × 10 ^-4mol / g, 2.99 × 10
^-4mol / g.

Synthesis Example 2Polylactic acid-modified polyester polyols (e) to (h)
Synthesis  One tank equipped with a stirrer, thermometer, cooling tube, and nitrogen inlet
After purging the 5-neck flask with nitrogen, self-dehydration
The weight-average molecular weight of which is increased by condensation to about 3,000
0, polylactic acid oligomer having a number average molecular weight of 1,160
100.0 g (0.0862 mol of carboxylic acid groups) and salt
Add 300 g of methylene chloride and dissolve, then add 2-chloro
-1,3-dimethylimidazolidinium chloride (hereinafter referred to as
17.48 g (0.103 m)
Le), 5.59 g of ethylene glycol, pentaerythri
0.91 g of tall (ethylene glycol and pentaeryth
Litol molar ratio is 9: 0.67, total 0.0967 mol
) And 24.12 g of β-picoline (0.259).
Mol) and stirred at 30-40 ° C. for 3 hours to carry out the reaction.
Was. After completion of the reaction, the reaction solution is diluted with a 30% hydrochloric acid aqueous solution
Was sequentially washed. Then, dichloromethane was added under reduced pressure.
Removed by heating, polylactic acid-modified polyester polyol 10
4.9 g were obtained. The yield was 100%. Obtained
Of polylactic acid-modified polyester polyol (e)
The weight average molecular weight obtained in the above is about 3,000, and the acid value is 1.1.
8 × 10^-5mol / g, hydroxyl value 1.88 × 10
^-3mol / g. Ethylene glycol and penta
The total number of moles of erythritol was 0.0580 mol, 0.1 mol.
Same as above except changing to 0290 mol and 0.0145 mol
Weight average molecular weight of about 5,000 based on the molar ratio of
(F) 10,000 (g) and 20,000 (h) points
A lactic acid-modified polyester diol was synthesized. Got
The hydroxyl value of the polylactic acid-modified polyester diol
1.21 × 10 each^-3mol / g, 6.11 × 10
^-4mol / g, 3.06 × 10^-4mol / g
Was.

Synthesis Example 3Synthesis of succinic polyester (i)  Equipped with stirrer, fractionating condenser, thermometer, nitrogen inlet tube
1,4-butane in a 3-liter separable flask
All 750 g, succinic acid 885 g and tetraisopro
1.6 g of piltitanate was charged and 195 to 195 in a nitrogen stream.
Esterified at 200 ° C. and finally 0.6 torr
The deglycolization reaction is performed under reduced pressure at 210 to 215 ° C for 6 hours.
went. As a result, the weight average molecular weight of
A citric acid-based polyester (i) was obtained. Cool to room temperature
Succinic polyester (i) is white, wax
And solidified. The melting point is 110-115 ° C.
Was.Synthesis of adipic acid-based polyester (j)  Equipped with the same equipment as in the above synthesis example of polyester (A)
1,4-butane in a 3-liter separable flask
750 g of diol, 1095 g of adipic acid and tetri
1.8 g of isopropyl titanate is charged and placed in a nitrogen stream.
Esterification at 90-200 ° C. for 6 hours, then finally
Is set to 0.5 torr under reduced pressure,
A deglycol reaction was performed for a time. The resulting weight average molecule
15,000 adipic acid-based polyester (j) was obtained.
Was. Adipic acid-based polyester cooled to room temperature (j)
Became a yellowish wax and solidified. Fusion
The point was about 58 ° C.

Synthesis Example 4Polylactic acid-modified polyester diol (k)-(m)
Success  Polymilk having a weight average molecular weight of 3,000 used in Synthesis Example 1
100.0 g of acid oligomer (0.086 carboxyl group)
2 mol) and 300 g of methylene chloride at 40 ° C.
Dissolve, then 0.90 g of 1,4-butanediol
(0.01 mol), 17.48 g of DMC (0.103
24) and β-picoline 24.12 g (0.259 mol)
Was added sequentially, and the reaction was carried out at 40 ° C. for 3 hours. End of reaction
After completion of the reaction, dilute the reaction solution to 10%, and sequentially add 30% hydrochloric acid and water.
Next, it is washed and concentrated with an evaporator to obtain methyl chloride.
Was removed. Of the obtained polyester diol (k)
The weight average molecular weight is 30,000 and the molecular weight distribution dispersity is
3.0. The amount of 1,4-butanediol used
Same as above except changing to 0.43g, 0.347g
The method was repeated to obtain a weight average molecular weight of 65,000 (l),
78,000 (m) polylactic acid-modified polyester dial
I got

Examples 1 to 4 100 g of the polylactic acid-modified polyester diol (a) having a weight average molecular weight of about 3,000 obtained in Synthesis Example 1 was added to 200
Charge into a flask of 100 ml and heat and melt. There, 19.8 g (0.096 mol) of stoichiometric NBDI was added to 30
The mixture is gradually added over a period of 1 minute and held for 1 hour to obtain a decomposable polyurethane resin having a melting point of 170 ° C. (hereinafter abbreviated as polyurethane resin). Hereinafter, Examples 2 to 4 and Comparative Example 1
, The molecular weight of the polyester diol used was 5,000 (polyol (b), Example 2), 1
0000 (polyol (c), Example 3), 20,000
Polyurethane resin is synthesized by changing to 00 (polyol (d), Example 4). In all of Examples 1 to 4, the weight average molecular weight reaches 100,000 or more. However, NBD
The amount of I used is 0.5 mol times the number of hydroxy groups of the polyol. 100 μm thick polyurethane resin
And the physical properties are measured. Table 1 shows various physical properties.

Example 5 50 g of a polylactic acid-modified polyester diol (a) having a molecular weight of 3,000 and a isocyanurate of NBDI obtained by the same method as in Synthesis Example 1 as a polyester diol were used. The mixture is charged into a flask in a molar amount, heated under a nitrogen stream, and stirred for 1 hour while being melted. This is discharged onto a stainless steel vat under nitrogen to obtain a polyurethane resin. Table 1 shows the physical properties of the obtained polyurethane resin.
Shown in

Example 6 A polyurethane resin is obtained according to Example 5, except that the NBDI uretondione is used as the modified NBDI. Table 1 shows the physical properties of the obtained polyurethane resin.

Example 7 The procedure of Example 5 was followed except that a NBDI bullet was used as the modified NBDI. Table 1 shows the physical properties of the obtained polyurethane resin.

Example 8 The procedure of Example 5 was followed, except that a trimethylolpropane adduct of NBDI was used as the modified NBDI. Table 1 shows the physical properties of the obtained polyurethane resin.

Example 9 The procedure of Example 5 was followed except that a carbodiimide having an average number of repeating units of 8 was used as the modified NBDI.
Table 1 shows the physical properties of the obtained polyurethane resin. A test piece obtained by melt-molding the obtained polyurethane resin at 240 ° C. has a heat deformation temperature of 171 ° C. and shows good heat resistance as a biodegradable resin.

Example 10 100 g of the polylactic acid-modified polyester polyol (e) having a weight average molecular weight of 3,000 obtained in Synthesis Example 2 was added to 200
Heat to ℃ to melt and add NBDI dropwise over 30 minutes. The amount of NBDI added is adjusted so that the number of isocyanate groups becomes stoichiometric with respect to the hydroxyl groups of the polylactic acid-modified polyester polyol. Thereafter, the mixture is stirred for 1 hour and discharged into a stainless steel vat under nitrogen to obtain a polyurethane resin. Table 1 shows various physical properties measured by preparing a press film in the same manner as in Example 1.

Example 11 The procedure of Example 10 was followed except that the polylactic acid-modified polyester polyol (f) having a weight average molecular weight of 5,000 obtained in Synthesis Example 2 was used. Table 1 shows properties of the obtained polyurethane resin.

Example 12 The procedure of Example 10 was followed except that the polylactic acid-modified polyester polyol having a weight average molecular weight of 10,000 obtained in Synthesis Example 2 was used. Table 1 shows properties of the obtained polyurethane resin.

Example 13 The procedure of Example 10 was followed except that the polylactic acid-modified polyester polyol having a weight average molecular weight of 20,000 obtained in Synthesis Example 2 was used. Table 1 shows properties of the obtained polyurethane resin.

Comparative Example 1 100 g of polylactic acid having a number average molecular weight of 1,500 was dissolved in 300 g of benzene, and 13.52 g (0.08 mol) of D was dissolved.
17.88 g (0.192 mol) of MC and β-picoline
Was stirred for several minutes and then allowed to stand for 2 hours. This solution is diluted to a concentration of 10%, washed sequentially with 30% hydrochloric acid and water, discharged into a large amount of isopropyl alcohol, filtered, and dried to obtain a polylactic acid powder. The weight average molecular weight of this polylactic acid is 193,000, which is a sufficient molecular weight to confirm physical properties. Table 1 shows the results of measuring the physical properties of this polylactic acid. According to this, all of the polylactic acid-based biodegradable polyurethane resins synthesized in Examples 1 to 13 were improved in mechanical properties as compared with polylactic acid, and were comparable to biodegradability. Further, the polymer sheet obtained by molding the polylactic acid obtained in Comparative Example 1 was bent at 180 degrees for one time.
Cracks and inflexibility only after repeated use.

Comparative Example 2 A weight-average molecular weight of 10, obtained by the same method as in Synthesis Example 1,
After charging 100 g of polylactic acid-modified polyester diol of 000 into a flask and heating to a molten state, 2.44 g of hexamethylene diisocyanate was charged and stirring was continued for 1 hour. The viscosity increases rapidly but does not gel. After completion of the reaction, the mixture was discharged into a stainless steel vat to obtain a polyurethane resin. Table 1 shows the results of measuring the physical properties of the obtained polyurethane resin by molding. According to this,
The polyurethane resin produced in Example 4 was comparable to the resin of the present comparative example in terms of biodegradability, and Example 4 was superior in mechanical properties.

Comparative Example 3 A weight-average molecular weight of 10, obtained by the same method as in Synthesis Example 1,
000 polylactic acid-modified polyester diol (c) 10
After charging 0 g to the flask and heating to a molten state, 3.98 g of isophorone diisocyanate was charged and stirring was continued for 1 hour. The increase in viscosity is slow, the molecular weight does not reach the same as in Example 4 even if stirring is continued for 6 hours, and the reaction rate is very slow. After completion of the reaction, the mixture was discharged into a stainless steel vat to obtain a polyurethane resin. Table 1 shows the results of measuring the physical properties of the obtained polyurethane resin by molding. According to this, the polyurethane resin produced in Example 4 was not inferior to the resin of this comparative example in biodegradability, and Example 4 was superior in mechanical properties. Further, the polymer sheet obtained by molding the polyurethane resin obtained in the present comparative example is broken by only one bending at 180 degrees, and is inferior in flexibility.

Biodegradability Table 1 shows the results of measuring the biodegradability of the polyurethane resins obtained in Examples 1 to 13 and Comparative Examples 1 to 3 in accordance with ISO / CD14855.

Tensile Test Table 1 shows the results of a tensile test performed on the polyurethane resins obtained in Examples 1 to 13 and Comparative Examples 1 to 3 in accordance with JIS K7113.

[0073]

[Table 1]

Example 14 A 1-liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer and a nitrogen introducing tube was charged with 400 g of the polyester (i) obtained in Synthesis Example 3 and 100 g of the polyester (j). Then, the mixture was heated and uniformly melted, the pressure was reduced to 1 torr for 10 minutes, the pressure was returned to normal pressure, and 9.09 g of NBDI was added at 200 ° C. in a nitrogen stream. The viscosity increases rapidly but does not gel. Stirring was continued for 30 minutes and discharged onto a stainless steel vat. The obtained polyurethane resin was formed into a pressed film having a thickness of 100 μm by a hot press machine. This film is tough and cannot be split manually. The tensile strength of the transparent film after being stretched three times in each direction was 75 MPa.

Example 15 1,4-butanediol 3 was placed in a 1-liter flask equipped with a stirrer, a distillation condenser, a nitrogen inlet tube, and a thermometer.
00g (3.33 mol), succinic acid 354 g (3.00 mol)
Mol), and esterified in a nitrogen stream at 200 to 205 ° C for 5 hours. Then, 0.06 g of tetraisopropyl titanate was added, and the condenser was changed to a direct storage type. 1 under the condition of 5 torr
After performing the deglycol reaction for 0 hour, the mixture was discharged into a metal vat. The obtained polyester diol is white, opaque and hard wax because of its crystallinity, and has a weight average molecular weight of 3
The acid value was 8,000, the acid value was 1.02 × 10 ⁻⁵ mol / g, and the hydroxyl value was 5.88 × 10 ⁻⁵ mol / g. Stirrer,
300ml equipped with condenser, nitrogen inlet tube and thermometer
The resulting aliphatic polyester diol 1
00g (hydroxyl group 5.88 × 10 ^-3 mol)
After melting at 180, 0.77 g of NBDI was added. The viscosity increases rapidly but does not gel. Thereafter, the reaction was continued for 1 hour and terminated. When the physical properties of the obtained aliphatic polyurethane were measured as a pressed film of 100 μm using a hot press machine, the mechanical properties were good, with a tensile strength at break of 68 MPa and an elongation at break of 490%.

Example 16 14.6 g of adipic acid was placed in a 100 ml four-necked flask.
(0.10 mol), 9.2 g of 1,4-butanediol,
0.3 g of DL-malic acid, 0.05 of methanesulfonic acid
g, and toluene (40 ml).
A dehydration condensation reaction was performed for a time. The molecular weight determined by GPC at this time was such that the number average molecular weight was 16,000 and the weight average molecular weight was 37,000. The hydroxyl value is 1.41 ×
It was 10 ^-4 mol / g. Then NBDI 0.32
g was added and reacted at 100 ° C. for 4 hours. The weight average molecular weight at this time was 161,000. After the reaction,
The toluene and methanesulfonic acid were removed under reduced pressure to obtain a modified polybutylene adipate.

Example 17 The weight average molecular weight obtained by the same method as in Synthesis Example 1 was 1
000 polylactic acid-modified polyester diol (c)
50 g and 200 g of xylene are charged into a flask and 100
After melting at ℃, 1.85 g of NBDI (8.95 × 10 ⁻³⁾
Mol) and 10 mg of 1,4-diaza [2.2.2] bicyclooctane were added and reacted for 2 hours. Then, 3-methyl-1-phenyl-3 which is a carbodiimidation catalyst is used.
120 ° C. with addition of 10 mg of phospholene oxide
For 20 hours. After completion of the reaction, the mixture was cooled and filtered,
After washing with 500 ml of methyl-t-butyl ether, 8
After drying under reduced pressure at 0 ° C. for 12 hours, a decomposable polyurethane carbodiimide was obtained. This polyurethane resin was molded at 240 ° C. using a hot press machine to prepare a 3 mm-thick press sheet. This Vicat softening point is calculated according to JIS K 720
6, the Vicat softening point was 174.
° C.

Example 18 40 g of cellulose acetate having a weight average molecular weight of 110,000, 60 g of the polylactic acid-modified polyester polyol (a) having a molecular weight of 5,000 obtained in Synthesis Example 1, and xylene 3
, And melt at 120 ° C. There, 1,4-diaza [2.2.2] bicyclooctane 1
% Xylene solution and then NBDI 11.8
g (0.057 mol) were charged and the reaction was continued for 1 hour. After completion of the reaction, the mixture was cooled, filtered, washed with 800 g of isopropyl alcohol, and dried at 80 ° C. under reduced pressure to obtain a polyurethane resin powder. The press film formed from this resin powder had a tensile strength at break of 69 MPa, an elongation of 260%, and a tensile modulus of elasticity of 3920 MPa.

Example 19 100 g of a polylactic acid-modified polyester diol (k) having a weight average molecular weight of 30,000 obtained in Synthesis Example 4 was dissolved by heating, stoichiometric NBDI was added, and the mixture was kept for 1 hour. A polyurethane resin was obtained. This polymer was extruded using an extruder equipped with a T die to a thickness of 800 μm.
m of unstretched film was obtained. Table 2 shows the physical properties of the obtained film.

Example 20 The procedure of Example 19 was followed except that the polylactic acid-modified polyester diol (l) having a weight average molecular weight of 65,000 obtained in Synthesis Example 4 was used. Table 2 shows the physical properties of the obtained film.

Example 21 The procedure of Example 19 was followed except that the polylactic acid-modified polyester diol (m) having a weight average molecular weight of 78,000 obtained in Synthesis Example 4 was used. Table 2 shows the physical properties of the obtained film.

Example 22 The polylactic acid-modified polyester diol (l) having a weight average molecular weight of 65,000 obtained in Synthesis Example 4 and polybutylene succinate having a weight average molecular weight of 50,000 were mixed at 90:10.
Example 19 was followed except that the mixture was used at a ratio of. Table 2 shows the physical properties of the obtained film.

Example 23 Polylactic acid-modified polyester diol having a weight average molecular weight of 78,000 obtained in Synthesis Example 4 and a weight average molecular weight of 5
The procedure was as in Example 19, except that polybutylene succinate of 000 was used in a ratio of 80:20. Table 2 shows the physical properties of the obtained film.

[0084]

[Table 2] Mw: weight average molecular weight X: polylactic acid-modified polyester diol Y: polybutylene succinate

Example 24 Example 1 was repeated except that the polylactic acid-modified polyester diol having a weight average molecular weight of 30,000 obtained in Synthesis Example 4 was used.
In the same manner as in 9, a polyurethane resin was obtained. The obtained polyurethane resin was processed into an unstretched sheet having a thickness of 1.2 mm using an extruder. The resulting polymer sheet is
Even when the bending at 180 ° C. was repeated 100 times, there was no crack and the flexibility was good.

Example 25 The procedure of Example 24 was followed except that the polylactic acid-modified polyester diol (l) having a weight average molecular weight of 65,000 obtained in Synthesis Example 4 was used. The resulting polymer sheet is 180
No cracking even after 100 ° C bending,
The flexibility was also good.

Example 26 The procedure of Example 24 was followed except that the polylactic acid-modified polyester diol (m) having a weight average molecular weight of 78,000 obtained in Synthesis Example 4 was used. The resulting polymer sheet is 180
When bending at a temperature of 89 ° C. was repeated 89 times, cracking occurred and the flexibility was also good.

Example 27 The polylactic acid-modified polyester diol (l) having a weight average molecular weight of 65,000 obtained in Synthesis Example 4 and polybutylene succinate having a weight average molecular weight of 50,000 were mixed with 90:
Example 24 was followed except that it was used at a ratio of 10.

Example 28 The polylactic acid-modified polyester diol (m) having a weight average molecular weight of 78,000 obtained in Synthesis Example 4 and the polybutylene succinate having a weight average molecular weight of 50,000 were combined with 8
Example 24 was followed except that it was used at a ratio of 0:20.

Example 29 A biodegradable resin was obtained in the same manner as in Example 19, and the obtained polymer was melt-spun and a staple filament was obtained using an extruder equipped with a nozzle. Table 3 shows the physical properties of the obtained staple filament.

Example 30 A polyurethane resin was obtained in the same manner as in Example 20, and the obtained polymer was melt-spun and staple filaments were obtained using an extruder equipped with a nozzle. Table 3 shows the physical properties of the obtained staple filament.

Example 31 A polyurethane resin was obtained in the same manner as in Example 21, and the obtained polymer was melt-spun and staple filaments were obtained using an extruder equipped with a nozzle. Table 3 shows the physical properties of the obtained staple filament.

[0093]

[Table 3] Mw: weight average molecular weight X: polylactic acid-modified polyester diol Y: polybutylene succinate

Example 32 1 g of each of the polyurethane resin powders obtained in Examples 1 to 18 was charged into a 10 ml sodium hydroxide aqueous solution (20 g) and a rotor into a 50 ml screw tube.
Stir with a magnetic stirrer in the temperature range of 0 ° C,
The hydrolyzability of each polyurethane resin powder was tested. All powders were hydrolyzed within one hour and dissolved in water.

[0095]

The decomposable polyurethane resin of the present invention is a kind of isocyanate compound, 2,5- /
2,6-diisocyanatomethylbicyclo [2.2.1]
A polyurethane resin using heptane and / or a modified product thereof as a binder for a degradable resin. This resin is a degradable, that is, a polyurethane resin having hydrolyzability and biodegradability, after using the resin for a desired purpose,
The raw material can be recovered by hydrolysis and reused. That is,
Even in areas where recycling is difficult such as printing paper combined with general-purpose resins, recycling can be promoted.For example, paper and cards laminated with the polyurethane resin of the present invention are separated from other general paper. Can be collected and recycled without waste. In addition, as a biodegradable resin, compared to conventionally known biodegradable resins, it also has excellent rigidity and elasticity, and also has flexibility, while having high strength,
It is possible to provide a resin molded product having biodegradability in addition to having new physical properties such as high elasticity and high elongation, which have not existed conventionally.
Therefore, the polyurethane resin of the present invention can be applied to a field in which conventional biodegradable resins have good biodegradability but are not sufficiently applicable in terms of physical properties. Also,
Compared with conventionally known biodegradable resins using aliphatic diisocyanate as a binder, it is obtained without imposing a large burden on production, and the diamine formed after decomposition has no mutagenicity, is safe and environmentally compatible High biodegradable resin.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) D01F 6/70 D01F 6/70 (72) Inventor Naoki Sato 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. F Terms (reference) 4F071 AA53 AF01 AF52 BB07 BB09 BC01 4J034 BA03 DA01 DB05 DC50 DF01 DF12 DF16 DF20 DF24 EA04 EA08 HA01 HA07 HA08 HB05 HB06 HB07 HB08 HC17 HC22 HC25 HC26 HC34 HC35 HC52 HC04 HC01 KB07 HC07 HC01 HC01 KB04 RA09 4L035 BB31 EE04 EE20 HH01 HH04 HH10 MH02 MH04 MH13

Claims (17)

[Claims] 1. A polyol and a compound represented by the formula (1): (Formula (1) represents a single or a mixture of a 2,5-substituted and a 2,6-substituted isocyanatomethyl group, respectively) 2,5- / 2,6-diisocyanatomethyl A polyurethane resin obtained by reacting bicyclo [2.2.1] heptane and / or a modified product thereof, wherein the polyol is (A) a polyhydroxycarboxylic acid polyol, (B) an aliphatic resin, One or a mixture of two or more selected from the group consisting of polyester polyols and (C) saccharides, or a polyol composed of a co-condensed polymer, or (D) (A) and / or (B) is trivalent or more A decomposable polyurethane resin which is a polyol that may be branched by condensation with an aliphatic polyhydric alcohol. 2. The polyhydroxycarboxylic acid polyol (A) is represented by the formula (2): (In the formula, R ¹ is an alkylene group having 1 to 4 carbon atoms in the straight chain portion, and represents an alkylene group having 1 to 6 carbon atoms including a branched alkyl group, and m is 1 or more. The decomposable polyurethane resin according to claim 1, wherein the terminal carboxyl group of the aliphatic polyhydroxycarboxylic acid represented by the following formula is modified into a hydroxy group. 3. In the formula (2), R ¹ is an alkylene group having 1 carbon atom, a methyl group having 1 carbon atom in a straight chain portion,
An alkylene group substituted with any of an ethyl group or a propyl group, an alkylene group substituted with a methyl group or an ethyl group having 2 carbon atoms in the straight-chain portion, or having 3 carbon atoms in the straight-chain portion; The alkylene group substituted by a methyl group, wherein the formula (2) is an aliphatic polyhydroxycarboxylic acid polyol in which R ¹ contains the same or two or more structural units. Polyurethane resin. 4. An aliphatic polyester polyol represented by the formula (3): (Wherein, R ² represents an optionally substituted aliphatic hydrocarbon group having 2 to 20 carbon atoms), and one or more selected from aliphatic polyhydric alcohols represented by formula (4) ) (Wherein R ³ represents an optionally substituted aliphatic hydrocarbon group having 2 to 20 carbon atoms) by reacting with one or more kinds selected from aliphatic polybasic acids represented by the formula: The decomposable polyurethane resin according to claim 1, which is obtained. 5. The decomposable polyurethane resin according to claim 1, wherein the saccharide is one or more compounds selected from monosaccharides, molasses, cellulose and cellulose derivatives. 6. A polyhydric alcohol having a valency of 3 or more is represented by the formula (5): (In the formula, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms. N is 3 to
An integer of 6. One or two selected from the compounds represented by
The decomposable polyurethane resin according to claim 1, which is at least one kind. 7. An acid value of the polyol is 10 ⁻⁴ mol / g.
The decomposable polyurethane resin according to claim 1, which is as follows. 8. A modified 2,5- / 2,6-diisocyanatomethylbicyclo [2.2.1] heptane is represented by the formula (6): An isocyanurate form of 2,5- and / or 2,6-diisocyanatomethylbicyclo [2.2.1] heptane represented by the following formula, or a block form thereof, represented by the formula (7): A uretdione form of 2,5- and / or 2,6-diisocyanatomethylbicyclo [2.2.1] heptane represented by the following formula, or a block form thereof, represented by the formula (8): A buret form of 2,5- and / or 2,6-diisocyanatomethylbicyclo [2,2,1] heptane represented by the formula or a block form thereof, represented by the formula (9): A trimethylolpropane adduct or a block thereof represented by the formula: ## STR10 ## 2. The decomposable polyurethane resin according to claim 1, wherein the polyurethane resin is at least one member selected from the group consisting of a polycarbodiimide compound represented by (Z is an integer of 1 or more). 3. 9. The amount of 2,5- / 2,6-diisocyanatomethylbicyclo [2.2.1] heptane and / or a modified product thereof is 0.001 to 40 with respect to the polyol.
The decomposable polyurethane resin according to claim 1, which is contained in a percentage by weight. 10. The hydrolyzable polyurethane resin according to claim 1. 11. The biodegradable polyurethane resin according to claim 1. 12. The polyol according to claim 1 and 2,5,
-/ 2,6-diisocyanatomethylbicyclo [2.2.
1] A decomposable polyurethane resin raw material composition comprising heptane and / or a modified product thereof. 13. A polymer film obtained by molding the decomposable polyurethane resin according to claim 1. 14. A polymer sheet obtained by molding the decomposable polyurethane resin according to claim 1. 15. A disk case base formed by molding the decomposable polyurethane resin according to claim 1. 16. A polymer staple obtained by molding the decomposable polyurethane resin according to claim 1. 17. A card base obtained by molding the decomposable polyurethane resin according to claim 1.