JPH09278994A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition comprising a reaction product obtained by mixing a specific oligomer with specific particles and subsequently reacting the mixture with a multifunctional isocyanate compound, excellent in tensile strength and tensile elongation in a temperature range above a room temperature, also excellent in biodegradability, low in cost, and useful for drinking tools, eating tools, etc. SOLUTION: This resin composition of obtained by mixing (A) 100 pts.wt. of an oligomer consisting mainly of a polyester and having an intrinsic viscosity of 0.1-0.9dl/g in o-chlorophenol at 30 deg.C [e.g. an oligomer comprising a compound of the formula: HOOC-Ru1 -COOH (R<1> is a 2-8C alkylene), a compound of the formula: HO-R<2> -OH (R<2> is a 2-6C alkylene) and a polyamide having a reducing viscosity of 0.5-7dl/g in a 1g/dl 98% sulfuric acid solution at 20 deg.C wherein the content of the polyamide is 3-50wt.%] with (B) a 50-900 pts.wt. of biodegradable organic particles and subsequently reacting the mixture with (C) 1-100 pts.wt. of multifunctional isocyanate compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent mechanical properties and biodegradability in a temperature range from room temperature to a practically high temperature.

[0002]

2. Description of the Related Art In recent years, environmental problems have been emphasized, and the increase of industrial waste has become a very serious problem. Most industrial wastes are molded plastic products, and biodegradable plastic materials are required. Conventionally, an aliphatic polyester has been known as a biodegradable plastic. However, this product was originally poor in heat resistance, had insufficient mechanical properties, etc., and was not practical.

Japanese Unexamined Patent Publication (Kokai) No. 7-149865 discloses a polyester resin which can be biodegraded by discarding it in soil and has practical properties. However, this product has a high cost and is insufficient in biodegradability.

[0004]

In view of the above, the present invention has an object to provide a resin composition which is excellent in mechanical properties and biodegradability in a temperature range from room temperature to a practically high temperature and which is low in cost. And

[0005]

The gist of the present invention is 100 parts by weight of an oligomer containing polyester as a main component and having an intrinsic viscosity (in o-chlorophenol, 30 ° C.) of 0.1 to 0.9 dL / g. On the other hand, the resin composition itself is obtained by mixing 50 to 900 parts by weight of biodegradable organic fine particles and then adding 1 to 100 parts by weight of a polyfunctional isocyanate compound and reacting them.

The resin composition of the present invention is obtained by mixing biodegradable organic fine particles with an oligomer containing polyester as a main component, and then adding a polyfunctional isocyanate compound and reacting it.

The intrinsic viscosity (in o-chlorophenol, 30 ° C.) of the above-mentioned polyester-based oligomer is
It is 0.1 to 0.9 dL / g. When it is less than 0.1 dL / g, the amount of the polyfunctional isocyanate compound for obtaining the high molecular weight resin composition increases, and the hardness of the obtained resin composition increases, so that the rubber elasticity becomes poor,
If it exceeds 0.9 dL / g, it is difficult to quantitatively proceed the chain extension reaction of the resin composition because the reactivity with the polyfunctional isocyanate compound is poor, and it is not possible to suppress the simultaneous crosslinking reaction. As a result, the resin composition produced has poor fluidity, and is therefore limited to the above range. It is preferably 0.2 to 0.5 dL / g.

The above-mentioned polyester-based oligomer contains polyester as a main component and has an intrinsic viscosity (o).
-In chlorophenol, 30 ° C) is 0.1-0.9d
It is not particularly limited as long as it is L / g, and examples thereof include those comprising a dicarboxylic acid component such as adipic acid and suberic acid, and a diol component such as butylene glycol, neopentyl glycol and propanediol. In the present invention, the polyesteramide oligomer can be preferably used from the viewpoint of mechanical properties of the obtained resin composition.

Examples of the above-mentioned polyesteramide oligomer include, for example, the general formula (1) HOOC-R ¹ -COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms).
At least one kind of dicarboxylic acids represented by the following general formula (2) HO—R ² —OH (2) (in the formula, R ² represents an alkylene group having 2 to 6 carbon atoms).
And at least one of the diols represented by and a polyamide.

The dicarboxylic acid represented by the above general formula (1) is not particularly limited, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid and the like can be mentioned. In the present invention, in addition to the dicarboxylic acid represented by the general formula (1), as a dicarboxylic acid component, an aromatic compound such as phthalic acid or maleic acid may be used as long as the physical properties of the molded product obtained from the resin composition are not impaired. Group-type dicarboxylic acids; various other carboxylic acids such as carboxylic acid-terminated polyols and carboxylic acid-terminated polyesters can be appropriately used in combination.
The blending amount of these is 5 to 2 with respect to the total dicarboxylic acid component amount including the dicarboxylic acid represented by the general formula (1).
It is preferably 0% by weight.

The diol represented by the general formula (2) is not particularly limited, and examples thereof include ethylene glycol and
1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl- 1,3-
Propanediol, 1-methyl-2-methyl-1,2-
Examples thereof include ethanediol, 1,1-dimethyl-1,2-ethanediol, 1-ethyl-1,2-ethanediol and the like. Of these, branched diols such as 1,2-propanediol and neopentyl glycol are preferable because they improve the flexibility of the polyesteramide oligomer produced.

In the present invention, as the diol component,
In addition to the diol represented by the general formula (2), an aliphatic diol such as glycol or polyalkylene oxide can be appropriately used in combination as long as the physical properties of the molded product obtained from the resin composition are not impaired.

The above glycol is not particularly limited,
For example, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1. , 3
-Diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like can be mentioned. These can be used alone or in combination of two or more.

The polyalkylene oxide is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide and the like. These can be used alone or in combination of two or more. The number average molecular weight of the polyalkylene oxide is 500 to 20.
000 is preferred. When it is less than 500, the flexibility of the produced polyester is insufficient, and when it exceeds 20,000, the physical properties such as thermal stability of the produced polyester are poor.

The amount of the glycol and the polyalkylene oxide compounded is 5 to 20% by weight based on the total amount of the diol components combined with the diol represented by the general formula (2).
It is preferred that

In the present invention, as the component constituting the polyesteramide oligomer, at least one of the dicarboxylic acids represented by the general formula (1) and the diol represented by the general formula (2) are used. At least one of them is used, but in this case, both the dicarboxylic acid represented by the general formula (1) and the diol represented by the general formula (2) do not have an alkyl chain in the side chain. It is preferable to use two or more of any one of these components. There is only one dicarboxylic acid represented by the above general formula (1) having no alkyl chain in the side chain and one diol represented by the above general formula (2) having no alkyl chain in the side chain. If only seed,
The crystallinity of the produced polyesteramide oligomer increases, and as a result, the resin composition obtained by using the produced polyesteramide oligomer as a constituent component has high hardness and poor rubber elasticity.

When two or more dicarboxylic acids represented by the above general formula (1) are used for the purpose of preventing the crystallinity of the produced polyesteramide oligomer from becoming too high as described above, they account for the entire dicarboxylic acid component. It is preferred that the proportion of any one dicarboxylic acid does not exceed 70% by weight. When any one kind of dicarboxylic acid is present in an amount of more than 70% by weight, the crystallinity of the produced polyesteramide oligomer is slightly increased, and as a result, the hardness of the obtained resin composition is increased and the rubber elasticity is inferior. Become. For the same purpose, when two or more diols represented by the general formula (2) are used, the proportion of any one diol in the whole diol component is 70% by weight.
Is preferably not exceeded.

In the above polyesteramide oligomer, as the polyester constituent component, the above-mentioned general formula (1) is used.
Is used as the dicarboxylic acid component, and the above-mentioned other dicarboxylic acid optionally used in combination is used as the dicarboxylic acid component, and the diol represented by the general formula (2) and the glycol, poly, or the like optionally used in combination. Alkylene oxide is used as the diol component.

In the polyester constituent component, the dicarboxylic acid component and the diol component are 1.2 to 3 of the diol component per mol of the dicarboxylic acid component.
It is preferable to charge it in a molar manner. If the amount of the diol component is less than 1.2 mols relative to 1 mol of the dicarboxylic acid component, the esterification reaction does not proceed efficiently, and if it exceeds 3 mols, an excess of the diol component is used, resulting in cost reduction. It is disadvantageous, and the cleavage reaction of the polyamide is likely to occur due to the excess diol component, so that the block property is lowered and the heat resistance is lowered.

The polyamide, which is the third component in the polyesteramide oligomer, has an amide bond in the polymer main chain, is dissolved in the dicarboxylic acid and diol which are the constituent components of the polyester, and
It can be heated and melted, and its reduced viscosity is 0.5 to
It is preferably 7 dL / g (1 g / dL 98% sulfuric acid solution, 20 ° C.). When the reduced viscosity is less than 0.5 dL / g, the polyamide block length of the obtained resin composition becomes short, and as a result, the mechanical strength of the obtained molded article at high temperature decreases, and when it exceeds 7 dL / g. However, the solubility is lowered and the synthesis becomes difficult. More preferably, it is 1 to 6 dL / g.

It is preferable that the polyamide has a degree of swelling in a mixed solution of toluene / isooctane = 1/1 (weight ratio) of 5.0% or less in terms of weight change rate.
If it exceeds 5.0%, the solvent resistance of the molded product obtained from the resulting resin composition is poor. The above polyamide has a molecular weight of 1
Those of 000 to 60,000 are preferable. Molecular weight 100
When it is less than 0, the polyamide segment length in the produced polyester oligomer is shortened, so that the block property is lowered, and the melting point of the obtained resin composition is lowered.
If it exceeds 0000, the solubility in the above-mentioned polyester constituent components is lowered and copolymerization becomes difficult. More preferably, it has a molecular weight of 2,000 to 50,000.

The above polyamide is not particularly limited,
For example, 4-nylon, 6-nylon, 6,6-nylon, 11-nylon, 12-nylon, 6,10-nylon, 6,12-nylon and other aliphatic nylons; isophthalic acid, terephthalic acid, metaxylylene diene Amine, 2,
2-bis (paraaminocyclohexyl) propane, 4,
4'-diaminodicyclohexylmethane, 2,2,4-
Examples thereof include polyamides obtained by polycondensing monomers such as trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine with aromatic, alicyclic, and side chain-substituted aliphatic monomers.

The content of the above polyamide in the above polyesteramide oligomer is preferably 3 to 50% by weight.
If it is less than 3% by weight, the mechanical strength of the molded product obtained from the resin composition produced will be insufficient, and if it exceeds 50% by weight, the hard segment content will increase and it will become hard,
A resin composition having good impact resistance cannot be obtained. More preferably, it is 5 to 30% by weight.

The above polyesteramide oligomer can be synthesized by an appropriate method, for example, by polymerization of the above dicarboxylic acid component and the above diol component in the presence of the above polyamide. The above-mentioned polymerization is usually carried out by advancing an esterification reaction as a first step and advancing a polycondensation reaction as a second step. In this case, it is preferable that the esterification reaction is carried out in a state of a transparent homogeneous solution by dissolving the polyamide in the polyester constituent component. The reaction does not proceed efficiently in a heterogeneous state. The melting temperature is preferably 150 to 230 ° C. If it is lower than 150 ° C, it is difficult to dissolve it, and if it exceeds 230 ° C, the ester-amide exchange reaction in which the polyester constituent component cleaves the polyamide chain becomes active, and as a result, the blockability of the resulting resin composition is impaired. Be done.

The above polycondensation reaction is preferably carried out under reduced pressure, preferably
It is preferably performed at 180 to 260 ° C. at 10 mmHg or less. If it is less than 180 ° C, the reaction rate is low,
Moreover, since the polymerization viscosity becomes high, efficient polymerization becomes difficult, and if the temperature exceeds 260 ° C., a decomposition reaction and coloring occur,
At the same time, the block property is impaired.

When synthesizing the above polyesteramide oligomer, a catalyst generally used in the production of polyester can be used. As such, for example, lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tungsten, tin, lead, antimony, arsenic, cerium, boron, Metals such as cadmium, manganese and zirconium; organometallic compounds thereof, organic acid salts, metal alkoxides, metal oxides and the like can be mentioned. Among these, calcium acetate, diacyl stannous, tetraacyl stannic acid, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyl titanate, tetrapropoxy titanate, titanium ( (Oxy) acetyl acetate, germanium dioxide,
Tungstic acid, antimony trioxide and the like are preferable. These can be used alone or in combination of two or more kinds.

In the resin composition of the present invention, after the biodegradable organic fine particles are mixed with the oligomer containing polyester as a main component, hydroxyl groups at both ends of the oligomer containing polyester as a main component and It can be obtained by a chain extension reaction with an isocyanate group of a functional isocyanate compound.

The biodegradable organic fine particles are not particularly limited, but starch is preferably used in the present invention. Since the above starch has excellent biodegradability, the biodegradability of the obtained resin composition can be improved. Moreover, even if it is mixed in a large amount, the fluidity of the obtained resin composition is not impaired. In the present invention, as the above-mentioned starch, tuber-derived ones or granular ones can be used. Further, those modified by esterification, etherification, etc. can also be used.

The above-mentioned starch is not particularly limited, and examples thereof include potato starch, tapioca starch, wheat starch, corn (mize) starch, and wax-like equivalents thereof.

The particle size of the above starch is preferably 50 μm or less. If it exceeds 50 μm, the mechanical strength of the molded product obtained from the resulting resin composition will be insufficient. More preferably, it is 30 μm or less. The amount of the above starch added is 100 oligomers containing the above polyester as a main component.
It is 50 to 900 parts by weight with respect to parts by weight. If it is less than 50 parts by weight, the biodegradability of the obtained resin composition is insufficient and it is also disadvantageous in terms of cost. If it exceeds 900 parts by weight, the fluidity of the obtained resin composition is lowered. However, since the moldability becomes insufficient, it is limited to the above range. The amount is preferably 100 to 600 parts by weight, more preferably 100 to 400 parts by weight.

The polyfunctional isocyanate compound is not particularly limited, and may be triphenylmethane triisocyanate or the like within a range that maintains the fluidity of the obtained resin composition.
A compound having more than one isocyanate group can be used, but diisocyanate is preferably used in the present invention.

The diisocyanate is not particularly limited as long as it is a compound having two isocyanate groups in the same molecule, and examples thereof include aromatic compounds such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate. Group diisocyanates; 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4
Examples thereof include butane diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, and hydrogenated 4,4′-diphenylmethane diisocyanate.

In the present invention, the compounding amount of the polyfunctional isocyanate compound is 1 to 100 parts by weight with respect to 100 parts by weight of the oligomer containing the polyester as a main component. If the amount is less than 1 part by weight, it is difficult to obtain a high molecular weight resin composition, and the mechanical strength of the obtained molded article decreases, and if it exceeds 100 parts by weight, excess isocyanate groups cause intermolecular crosslinking. The fluidity of the resin composition produced by the reaction is inferior, so that the range is limited. It is preferably 2 to 30 parts by weight, and more preferably 5 to 20 parts by weight.
Parts by weight. In the present invention, the compounding amount of the polyfunctional isocyanate compound is preferably 0.9 to 1.2 mol of the polyfunctional isocyanate compound with respect to 1 mol of the oligomer containing the polyester as a main component, More preferably, it is 0.95 to 1.1 mol.

The resin composition of the present invention can be obtained by adding and mixing the above-mentioned polyfunctional isocyanate compound to a mixture of the above-mentioned oligomer containing polyester as a main component and the above-mentioned starch and reacting them. The above polyfunctional isocyanate compound can be added and mixed using a kneader such as a kneader or an extruder. In this case, the mixing temperature is preferably 60 to 240 ° C. If the temperature is lower than 60 ° C, it is difficult to obtain a high molecular weight resin composition because the reactivity is low, and a resin composition having sufficient strength cannot be obtained. Also, the polyfunctional isocyanate compound is decomposed, and a resin composition having sufficient strength cannot be obtained. More preferably, it is 100 to 220 ° C.

A catalyst can be used during the above reaction. Examples of the catalyst include diacyl stannous tin, tetraacyl stannic tin, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate,
Tin tetraacetate, triethylene amine, diethylene amine, triethyl amine, naphthenic acid metal salt, octyl acid metal salt, triisobutyl aluminum, tetrabutyl titanate, calcium acetate, germanium dioxide,
Antimony trioxide and the like can be mentioned. These can be used alone or in combination of two or more kinds.

Polycarbodiimide may be added to the resin composition of the present invention in order to improve the heat resistance deterioration and water resistance resistance of the above polyester constituents and to improve the durability of the resulting molded article. As the polycarbodiimide, one having an average of 1 to 20 carbodiimide groups in one molecule is preferable. When the number of carbodiimide groups is less than 1 on average in one molecule, the resulting molded product has insufficient heat deterioration resistance and water deterioration resistance, and when it exceeds 20,
Since the reaction proceeds during mixing and the fluidity decreases, a good molded product cannot be obtained. More preferably, it is 1 to 10 on average in one molecule.

Examples of the polycarbodiimide include, for example, poly (1,3,5-triisopropylphenylene-
2,4-carbodiimide), poly (1,3-diisopropylphenylene-2,4-carbodiimide) and the like.

The amount of the polycarbodiimide added is appropriately varied depending on the number of carbodiimide groups present in one molecule, but is 0.1 to 20 parts by weight with respect to 100 parts by weight of the above-mentioned polyester-based oligomer. Parts are preferred.
If it is less than 0.1 parts by weight, the effect of the addition of the polycarbodiimide will not be exhibited, and if it exceeds 20 parts by weight, the reaction will proceed during mixing, the fluidity will be reduced, and the mechanical strength of the obtained molded article will be low. descend. More preferably, it is 1 to 10 parts by weight.

If desired, a stabilizer may be further used in the resin composition of the present invention. As the stabilizer,
For example, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzen, 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl} -2,4,8, 1
Hindered phenolic antioxidants such as 0-tetraoxaspiro [5,5] undecane; tris (2,4-di-
t-butylphenyl) phosphite, trilaurylphosphite, 2-t-butyl-α- (3-t-butyl-4)
-Hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dimyristyl-3,3'-
Thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerystyryl tetrakis (3
-Lauryl thiopropionate), ditridecyl-3,
A heat stabilizer such as 3'-thiodipropionate may, for example, be mentioned.

The resin composition of the present invention contains fibers, inorganic fillers, and
You may add additives, such as a flame retardant, a ultraviolet absorber, an antistatic agent, an inorganic substance, and a higher fatty acid salt. As the fiber,
For example, glass fiber, carbon fiber, boron fiber, silicon carbide fiber, alumina fiber, amorphous fiber, silicon
Inorganic fibers such as titanium / carbon fibers; organic fibers such as aramid fibers. Examples of the inorganic filler include calcium carbonate, titanium oxide, mica, talc and the like. Examples of the flame retardant include hexabromocyclododecane, tris- (2,3-dichloropropyl) phosphate, pentabromophenyl allyl ether, and the like.

Examples of the ultraviolet absorber include p-
t-butylphenyl salicylate, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-methoxy2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone and the like can be mentioned. Examples of the antistatic agent include N, N-bis (hydroxyethyl) alkylamine, alkylallyl sulfonate,
Alkyl sulfanates and the like can be mentioned. Examples of the inorganic substances include calcium carbonate, fly ash, dehydrated sludge, barium sulfate, alumina, silicon oxide, talc and the like.

Examples of the higher fatty acid salt include sodium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, sodium palmitate and the like. The amount of the higher fatty acid salt added is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the oligomer containing the polyester as a main component. If the amount is less than 0.1 parts by weight, the resin composition produced will be inferior in mold releasability, and the resulting molded product will be distorted. More preferably, it is 1 to 10 parts by weight.

The resin composition of the present invention can be used by mixing it with other thermoplastic resins, rubber components and the like to modify its properties. As the thermoplastic resin, for example, polyolefin, modified polyolefin, polystyrene, polyvinyl chloride, polyamide, polycarbonate,
Examples thereof include polysulfone and polyester. Examples of the rubber component include natural rubber, styrene-butadiene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer (EPM, EPDM), polychloroprene, butyl rubber, acrylic rubber, Examples thereof include silicone rubber, urethane rubber, olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, ester-based thermoplastic elastomer, and amide-based thermoplastic elastomer.

The resin composition of the present invention can be formed into a molded product by a commonly used molding method such as press molding, extrusion molding, injection molding or blow molding. In this case, the molding temperature varies depending on the melting point of the resin composition of the present invention and the molding method, but is generally preferably 130 to 280 ° C. If the temperature is lower than 130 ° C, the fluidity of the resin composition will be low, and a uniform molded article cannot be obtained. If the temperature exceeds 280 ° C,
The resin composition is decomposed and a molded product having sufficient strength cannot be obtained.

The resin composition of the present invention is, for example, food and drink, industrial parts, automobile parts, films, sheets, non-woven fabrics, nets, bags, containers, tapes, synthetic papers, tubes, sports goods, medical goods and the like. Can be suitably applied to the field.

The eating and drinking tool is not particularly limited, and examples thereof include forks, spoons, disposable chopsticks, straws and knives. The industrial parts are not particularly limited, for example, hydraulic hoses, coil tubes, sealing materials,
Examples include packing, V-belts, rolls, anti-vibration damping materials, shock absorbers, couplings, diaphragms and the like. The automobile member is not particularly limited, and examples thereof include boots such as constant velocity joint boots and rack and pinion boots; ball joint seals; safety belt parts; bumper facias; emblems; The film is not particularly limited, and examples thereof include a greenhouse cover film, a plant protection cover film, a soil protection cover film, a weed seed germination prevention film, and an agricultural mulch film.

The above-mentioned sheet is not particularly limited, and examples thereof include insect repellent sheets, light-shielding sheets, frost-preventing sheets, wind-preventing sheets, agricultural crop storage sheets and the like; masking sheets and the like. The non-woven fabric is not particularly limited, and examples thereof include non-woven fabrics for agriculture for the purpose of heat retention, weed control, light shielding, and the like. The net is not particularly limited, and examples thereof include bird nets, windbreak nets, vine nets such as cucumbers, and agricultural nets such as nets for preventing grazing from falling. The bags are not particularly limited, and examples thereof include a fertilizer bag, a rice bag, and a garbage collection bag. The container is not particularly limited, and examples thereof include a cup, a tray, a plate, and a pot for gardening.

The above-mentioned tape is not particularly limited, and examples thereof include a packaging tape, a self-binding binding tape, and an adhesive tape. The synthetic paper is not particularly limited,
For example, kraft paper, carton paper, glassine paper, coated paper, art paper, Kurpac paper, acid resistant paper and the like can be mentioned.
The tube is not particularly limited, for example, food,
Examples include tubes for toothpaste, pastes such as cosmetics, and the like. The sports equipment is not particularly limited, and examples thereof include shoe soles and balls for ball games. The medical supplies are not particularly limited, and examples thereof include medical tubes, blood transfusion packs, catheters, syringes and the like. In addition to the above applications, it can be suitably used as a packing band, elastic fiber, elastic sheet, composite sheet, hot melt adhesive, material for alloying with other resins, and the like.

The present invention 2 includes the general formula (3) HOOC-R ³ —COOH (3) (wherein R ³ represents an alkylene group having 2 to 8 carbon atoms).
And at least one of the dicarboxylic acids represented by the general formula (4) HO—R ⁴ —OH (4) (wherein R ⁴ represents an alkylene group having 2 to 6 carbon atoms).
To 100 parts by weight of the polyester constituent component consisting of at least one of the diols represented by
dL98% sulfuric acid solution, 20 ° C.) 0.5 to 7 dL / g of polyamide 3 to 250 parts by weight are dissolved, and the esterification reaction of the above polyester constituents is conducted at 150 to 230 ° C.
Resin composition obtained by mixing 50 to 900 parts by weight of biodegradable organic fine particles with 100 parts by weight of polyesteramide obtained by polymerizing at 180 to 260 ° C. under reduced pressure. It is a thing.

In the second aspect of the present invention, first, a polyester comprising at least one dicarboxylic acid represented by the general formula (3) and at least one diol represented by the general formula (4). Polyamide is dissolved in the constituent components, and the esterification reaction of the polyester constituent components is performed.

The dicarboxylic acid represented by the above general formula (3) is not particularly limited, and examples thereof include the same as those exemplified as the dicarboxylic acid represented by the general formula (1) in the present invention 1. be able to. The diol represented by the general formula (4) is not particularly limited, and examples thereof include the same ones exemplified as the diol represented by the general formula (2) in the first invention.

In the second aspect of the present invention, a branching agent such as a polyol, polycarboxylic acid or oxyacid is added to the above polyester constituents for the purpose of increasing the molecular weight of the obtained polyesteramide, increasing the viscosity and shortening the polymerization time. be able to.

The above-mentioned polyol is not particularly limited,
For example, glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakishydroxymethylcyclohexane, tris (2-hydroxyethyl).
Examples thereof include isocyanurate and dipentaerythritol.

The polycarboxylic acid is not particularly limited, and examples thereof include hemimellitic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid and the like. These can be used alone or
More than one species can be used in combination.

The above-mentioned oxyacid is not particularly limited, and examples thereof include citric acid, tartaric acid, 3-hydroxyglutaric acid,
4-β-hydroxyethylphthalic acid and the like can be mentioned. These can be used alone or in combination of two or more.

The amount of the branching agent added is determined by the above general formula (3).
0.1 to 100 mol of the dicarboxylic acid represented by
2.5 mol is preferred. When it is less than 0.1 mol, the effect of increasing the molecular weight of the obtained polyesteramide is small,
It is not possible to obtain a resin composition having excellent mechanical strength,
When it exceeds 2.5 mol, gelation occurs.

In the second aspect of the present invention, aromatic dicarboxylic acids and aromatic diols can be used as the polyester constituent components as long as the flexibility of the obtained polyesteramide is not impaired.

The aromatic carboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, metal salts of 5-sulfoisophthalic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether,
4,4'-dicarboxydiphenyl sulfide, 4,
4'-dicarboxydiphenyl sulfone, 3,3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ethane, 1,4-dicarboxynaphthalene, 2,6
-Dicarboxynaphthalene and the like.

The aromatic diol is not particularly limited, and examples thereof include hydroquinone, resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4'-dihydroxybiphenyl,
4,4'-dihydroxydiphenyl ether, 4,4 '
-Dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, bisphenol A, 1,1-di (4-hydroxyphenyl) cyclohexane, 1,2- Examples thereof include bis (4-hydroxyphenoxy) ethane and 1,4-dihydroxynaphthalene.

The polyamide is not particularly limited,
For example, the same ones as exemplified in the first aspect of the invention can be cited. In the present invention 2, the reduced viscosity of the polyamide is 0.5 to 7 dL / g (1 g / dL
98% sulfuric acid solution, 20 ° C). If it is less than 0.5 dL / g, the mechanical strength of the resulting resin composition at high temperature will be insufficient, and if it exceeds 7 dL / g, the solubility of the above-mentioned polyamide in the above-mentioned polyester constituent components will decrease and synthesis will be difficult. Therefore, it is limited to the above range. Preferably,
It is 1 to 6 dL / g. The molecular weight of the polyamide is preferably 10,000 to 60,000, more preferably 20,000 to 50,000.

The amount of the polyamide compounded is 3 to 250 parts by weight per 100 parts by weight of the polyester constituent component. If it is less than 3 parts by weight, the mechanical strength of the molded product obtained from the produced polyesteramide will be insufficient, and if it exceeds 250 parts by weight, the nylon will be difficult to dissolve and the polymerization reaction will be difficult to proceed. Limited to It is preferably 3 to 200 parts by weight, more preferably 3
~ 180 parts by weight.

The esterification reaction of the polyester constituents is carried out by dissolving the polyamide in the polyester constituents in the state of a transparent homogeneous solution. The reaction does not proceed efficiently in a heterogeneous state.

In the present invention 2, the melting temperature is 1
It is 50-230 degreeC. When the temperature is lower than 150 ° C, it is difficult to dissolve the polyamide, and when the temperature is higher than 230 ° C, a decomposition reaction occurs, so the content is limited to the above range. The temperature is preferably 170 to 220 ° C.

In the present invention 2, after the above esterification reaction, a polymerization condensation reaction is allowed to proceed to obtain a polyesteramide. The polycondensation reaction is performed under reduced pressure, preferably 5 mm
It is performed at 180 to 260 ° C. under Hg or less. When the temperature is lower than 180 ° C, the reaction rate is low and the polymerization viscosity is high, so that efficient polymerization is difficult. When the temperature is higher than 260 ° C, a decomposition reaction and coloration occur, so the range is limited to the above range. The temperature is preferably 190 to 250 ° C.

A catalyst can be used when synthesizing the above polyesteramide. The catalyst is not particularly limited, and examples thereof include the same as those exemplified in the first aspect of the invention.

In the second aspect of the present invention, the content of the polyamide in the polyesteramide obtained as described above is preferably 3 to 90% by weight. If it is less than 3% by weight, the mechanical strength of the molded product obtained from the produced polyesteramide will be insufficient, and if it exceeds 90% by weight, the resulting resin composition will be non-uniform. More preferably 5-80
% By weight.

In the present invention 2, the intrinsic viscosity (in o-chlorophenol, 30 ° C.) of the polyester amide obtained as described above is preferably 0.6 to 2.7 dL / g. If it is less than 0.6 dL / g, the mechanical strength of the obtained molded article will be insufficient, and if it exceeds 2.7 dL / g, the fluidity will decrease due to the high viscosity, and melt molding will be difficult. More preferably, it is 0.8 to 2.0 dL / g.

The resin composition of the present invention 2 is obtained by mixing the polyesteramide with biodegradable organic fine particles. The biodegradable organic fine particles are not particularly limited, and examples thereof include the same as those exemplified in the first aspect of the invention. The amount of the biodegradable organic fine particles to be blended is the same as in the case of the present invention 1.

The method for mixing the polyesteramide and the biodegradable organic fine particles is not particularly limited, and for example, a method using a kneader such as a kneader, a plastomill, a roll, or an extruder may be employed. it can. In this case, the mixing temperature is preferably 150 to 240 ° C. When the temperature is lower than 150 ° C, the melt viscosity of the polyester amide becomes high, so that it becomes difficult to mix the polyesteramide and 240 ° C.
When it exceeds, the polyesteramide and the biodegradable organic fine particles are decomposed, and a resin composition having sufficient strength cannot be obtained.

Polycarbodiimide can be added to the resin composition of the present invention 2 mainly for the purpose of improving the water resistance and heat resistance of the above polyester constituent components as long as the biodegradability is not impaired. The polycarbodiimide is not particularly limited, and examples thereof include the same as those exemplified in the first aspect of the invention. The addition amount of the above polycarbodiimide is the same as in the case of the present invention 1.

If desired, the resin composition of the present invention 2 may contain
In addition, stabilizers may be used. The stabilizer is not particularly limited, and examples thereof include the same as those exemplified in the first aspect of the present invention.

In the resin composition of the present invention 2, fibers, inorganic fillers, flame retardants, ultraviolet absorbers, antistatic agents, inorganic substances, higher fatty acid salts, etc. are added to the resin composition at the time of or after the production, as long as the practicality is not impaired. You may add the additive of. These are not particularly limited, and examples thereof include the same as those exemplified in the first aspect of the present invention. The method for forming the resin composition of the present invention 2 into a molded body is not particularly limited, and, for example, the same method as in the case of the present invention 1 can be adopted.

The resin composition of the present invention 2 is, for example, food and drink, industrial parts, automobile parts, films, sheets, non-woven fabrics, nets, bags, containers, tapes, synthetic papers, tubes, sports goods, medical goods. It can be suitably applied to such fields.

[0074]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 146 parts by weight of adipic acid, 108 parts by weight of butylene glycol, 125 parts by weight of neopentyl glycol (butylene glycol / neopentyl glycol = 50/50 (molar ratio), dicarboxylic acid component / diol component at the time of charging =
1 / 2.4 (molar ratio), Toyobo Co., Ltd. 6-nylon (T850, 98% sulfuric acid, reduced viscosity at 20 ° C. 3.5.
dL / g) 20 parts by weight, tetrabutyl titanate 0.25 part by weight as a catalyst, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-) as a stabilizer.
0.4 parts by weight of 4-hydroxybenzyl) benzene and 0.4 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added, and the reaction system was heated to 200 ° C. under nitrogen. After 10 minutes, the nylon dissolved and became a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the esterification reaction proceeds, 20
The temperature was raised to 240 ° C. over a minute, and a pressure reduction operation was performed. The polymerization system reached a reduced pressure of 1 mmHg or less in 10 minutes. In this state, a polycondensation reaction was performed for 20 minutes to obtain 227 parts by weight of a transparent polyester-based oligomer.

The intrinsic viscosity of the obtained polyester-based oligomer was measured using an Ubbelohde viscometer in o-chlorophenol at 30 ° C.
It was 0.18 dL / g. To 100 parts by weight of the obtained polyester-based oligomer, 300 parts by weight of corn starch (PA # 220, average particle size 15 μm, manufactured by Nippon Food Processing Co., Ltd.) was added, and after kneading at 180 ° C. for 5 minutes , 4,4′-diphenylmethane diisocyanate (12 parts by weight) was added, and the mixture was kneaded for 7 minutes at 180 ° C. using a Brabender Plastograph extruder. Further, poly (1,3,5-triisopropylphenylene) was added as polycarbodiimide. 2,4-carbodiimide) (Stavaxol P-100, manufactured by Sumitomo Bayer Urethane Co., Ltd.) (2 parts by weight) was added and kneaded for 1 minute, and then extruded to obtain a resin composition. The obtained resin composition was made into a No. 3 dumbbell test piece by injection molding (injection pressure 1500 kgf / cm ² , mold temperature 70 ° C., cylinder temperature 200 ° C.), and the physical properties of the obtained test piece are described below. It was evaluated by. The results are shown in Table 1.

Evaluation method 1. Tensile breaking strength, tensile breaking elongation Measured at room temperature (23 ° C) and 150 ° C according to JIS K6301. 2. Content of Polyamide in Oligomer Containing Polyester as Main Component It was calculated from the weight of polyamide at the time of preparation with respect to the weight of the oligomer containing polyester as a main component. 3. Evaluation of biodegradability Based on JIS K 6950, the degree of biodegradation after 28 days in a room temperature (23 ° C) environment was measured by the BOD value.

Example 2 Adipic acid 58.4 parts by weight, suberic acid 104.5 parts by weight (adipic acid / suberic acid = 40/60 (molar ratio)), butylene glycol 130 parts by weight, 1,2-propanediol 73 Parts by weight (butylene glycol / 1,
2-propanediol = 60/40 (molar ratio), dicarboxylic acid component at the time of charging / diol component = 1 / 2.4 (molar ratio), 6-nylon manufactured by Toyobo Co., Ltd. (T850, 98)
% Reduced sulfuric acid at 20 ° C. 3.5 dL / g) 40 parts by weight, tetrabutyl titanate 0.25 part by weight as a catalyst, 1,3,5-trimethyl-2,4,6 as a stabilizer
0.4 parts by weight of tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (2,4-di-
0.4 parts by weight of (t-butylphenyl) phosphite was added, and the reaction system was heated to 200 ° C. under nitrogen. After 10 minutes, the nylon dissolved and became a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. Polymerization system is 1m in 10 minutes
The degree of reduced pressure reached mHg or less. As a result of polycondensation reaction for 30 minutes in this state, 251 parts by weight of a transparent polyester-based oligomer was obtained.

When the intrinsic viscosity of the obtained oligomer containing polyester as a main component was measured in the same manner as in Example 1, it was [η] = 0.30 dL / g. Corn starch (PA # 220, average particle size 15 μm) was obtained based on 100 parts by weight of the obtained polyester-based oligomer.
m, manufactured by Nippon Food Processing Co., Ltd.)
After kneading at 5 ° C for 5 minutes, 7 parts by weight of 4,4'-diphenylmethane diisocyanate was added, and kneading was performed at 180 ° C for 10 minutes using a Brabender Plastograph extruder,
Add 0.2 parts by weight of sodium stearate and add 1
After kneading for a minute, it was extruded to obtain a resin composition. Test pieces were prepared from the obtained resin composition in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Example 3 Instead of 20 parts by weight of 6-nylon (T850, manufactured by Toyobo Co., Ltd.), 6-nylon (A1050, in 98% sulfuric acid, 2
(Reduced viscosity at 0 ° C., 6.2 dL / g, manufactured by Unitika Ltd.) 65
272 parts by weight of an oligomer having a polyester as a main component was prepared in the same manner as in Example 1 except that 1 part by weight was used and the polycondensation reaction time after reaching a degree of reduced pressure of 1 mmHg or less was 40 minutes. Obtained. When the intrinsic viscosity of the obtained oligomer whose main component was polyester was measured in the same manner as in Example 1, it was [η] = 0.40 dL / g.

100 parts by weight of the obtained polyester-based oligomer was added to corn starch (PA # 2
890 parts by weight (20, average particle size 15 μm, manufactured by Japan Food Processing Co., Ltd.) and kneaded at 180 ° C. for 5 minutes, and then 4,4 ′
4.5 parts by weight of diphenylmethane diisocyanate were added and 1 using a Brabender Plastograph extruder
After kneading at 95 ° C. for 2 minutes, 5 parts by weight of magnesium stearate was further added and kneading for 2 minutes, and then extruded to obtain a resin composition. Test pieces were prepared from the obtained resin composition in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Example 4 100 parts by weight of the oligomer containing polyester as the main component obtained in Example 3 was added to corn starch (PA # 2
(20, average particle size 15 μm, manufactured by Japan Food Processing Co., Ltd.) 51 parts by weight was added, and the mixture was kneaded at 180 ° C. for 5 minutes, and then 4,4′-
Add 1.95 parts by weight of diphenylmethane diisocyanate and use a Brabender Plastograph extruder to add 1
Knead at 80 ° C for 5 minutes, and then add calcium stearate 4
After adding a weight part and kneading for 5 minutes, it extruded and obtained the resin composition. Test pieces were prepared from the obtained resin composition in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Example 5 In the same manner as in Example 1 except that 6-nylon was not added, 207 parts by weight of a transparent polyester-based oligomer as a main component was obtained. When the intrinsic viscosity of the obtained oligomer containing polyester as a main component was measured in the same manner as in Example 1, it was [η] = 0.18 dL / g.

100 parts by weight of the obtained polyester-based oligomer was added to corn starch (PA #
220, average particle size 15 μm, manufactured by Nippon Food Processing Co., Ltd.) 300
Parts by weight and 4.5 parts by weight of 1,4-butanediol are added, and after kneading at 180 ° C. for 5 minutes, 40 parts by weight of 4,4′-diphenylmethane diisocyanate are added and a Brabender Plastograph extruder is added. The mixture was kneaded at 180 ° C. for 5 minutes, 5 parts by weight of magnesium stearate was further added and kneaded for 2 minutes, and then extruded to obtain a resin composition. Test pieces were prepared from the obtained resin composition in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Example 6 211 parts by weight of a transparent polyester-based oligomer were obtained in the same manner as in Example 2 except that 6-nylon was not added. When the intrinsic viscosity of the obtained oligomer containing polyester as a main component was measured in the same manner as in Example 1, it was [η] = 0.28 dL / g.

With respect to 100 parts by weight of the obtained polyester-based oligomer, corn starch (PA #
220, average particle size 15 μm, manufactured by Japan Food Processing Co., Ltd.) 50 parts by weight, and 1,4-butanediol 5.2 parts by weight were added, and after kneading at 180 ° C. for 5 minutes, 4,4′-diphenylmethane diisocyanate was added. 40 parts by weight were added, and the mixture was mixed at 5 ° C at 180 ° C using a Brabender Plastograph extruder.
After kneading for 5 minutes, 5 parts by weight of magnesium stearate was further added and kneading for 2 minutes, and then extruded to obtain a resin composition. Test pieces were prepared from the obtained resin composition in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Example 7 207 parts by weight of a transparent polyester-based oligomer was obtained in the same manner as in Example 3 except that 6-nylon was not added. When the intrinsic viscosity of the obtained oligomer containing polyester as a main component was measured in the same manner as in Example 1, it was [η] = 0.42 dL / g.

With respect to 100 parts by weight of the obtained polyester-based oligomer, corn starch (PA #
220, average particle size 15 μm, manufactured by Japan Food Processing Co., Ltd.) 850
Parts by weight and 3.5 parts by weight of 1,4-butanediol, and kneading at 180 ° C. for 5 minutes, 20 parts by weight of 4,4′-diphenylmethane diisocyanate were added, and a Brabender Plastograph extruder was used. The mixture was kneaded at 180 ° C. for 5 minutes, 5 parts by weight of magnesium stearate was further added and kneaded for 2 minutes, and then extruded to obtain a resin composition. Test pieces were prepared from the obtained resin composition in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Comparative Example 1 227 parts by weight of an oligomer containing a polyester as a main component was prepared in the same manner as in Example 1 except that the polycondensation reaction time after the polymerization system reached a reduced pressure of 1 mmHg or less was 50 minutes. Obtained. When the intrinsic viscosity of the obtained oligomer having a polyester as a main component was measured in the same manner as in Example 1, it was [η] = 0.94 dL / g.

100 parts by weight of the obtained polyester-based oligomer was added to corn starch (PA #
220, average particle size 15 μm, manufactured by Nippon Food Processing Co., Ltd.) 300
After adding 1 part by weight and kneading at 180 ° C. for 5 minutes,
Add 12 parts by weight of 4'-diphenylmethane diisocyanate and use a Brabender Plastograph extruder to
The mixture was kneaded at 180 ° C. for 7 minutes, and poly (1,3,5-triisopropylphenylene) was added as polycarbodiimide.
2,4-carbodiimide) (STABAXOL P-10
0, made by Sumitomo Bayer Urethane Co., Ltd.) 1 part by adding 2 parts by weight
After kneading for a minute, it was extruded to obtain a resin composition. Test pieces were prepared from the obtained resin composition in the same manner as in Example 1 and evaluated. The results are shown in Table 1.

Comparative Example 2 146 parts by weight of adipic acid, 216 parts by weight of butylene glycol (dicarboxylic acid component / diol component at the time of charging = 1)
/2.4 (molar ratio)), 6-nylon (T
850, 98% sulfuric acid, reduced viscosity at 20 ℃ 3.5dL
/ G) 30 parts by weight, 0.25 parts by weight of tetrabutyl titanate as a catalyst, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4- as a stabilizer)
(Hydroxybenzyl) benzene 0.4 part by weight, tris (2,4-di-t-butylphenyl) phosphite 0.1 part by weight.
4 parts by weight was added, and the reaction system was heated to 200 ° C. under nitrogen. After 10 minutes, the nylon dissolved and became a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. The polymerization system reached a degree of reduced pressure of 1 mmHg or less in 10 minutes. As a result of polycondensation reaction for 30 minutes in this state, 230 parts by weight of a transparent polyester-based oligomer was obtained. The intrinsic viscosity of the obtained polyester-based oligomer was measured in the same manner as in Example 1 to find that [η] = 0.3.
It was 1 dL / g.

100 parts by weight of the obtained polyester-based oligomer was added to corn starch (PA #
220, average particle size 15 μm, manufactured by Nippon Food Processing Co., Ltd.) 950
After adding 1 part by weight and kneading at 180 ° C for 5 minutes, 1,4
-Butanediol (3 parts by weight) and 4,4'-diphenylmethane diisocyanate (9 parts by weight) were added, and the mixture was kneaded for 5 minutes at 180 ° C using a Brabender Plastograph extruder, and 0.3 parts by weight of calcium stearate was further added. After adding and kneading for 1 minute, it was extruded to obtain a resin composition. The obtained resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1. Since a uniform test piece could not be obtained, the tensile breaking strength and tensile breaking elongation were not evaluated.

Comparative Example 3 226 parts by weight of an oligomer having a polyester as a main component was prepared in the same manner as in Example 1 except that the polycondensation reaction time after the polymerization system reached a reduced pressure of 1 mmHg or less was 5 minutes. Obtained. The intrinsic viscosity of the obtained polyester-based oligomer was measured in the same manner as in Example 1.
[Η] = 0.09 dL / g.

300 parts by weight of corn starch (PA # 220, average particle size 15 μm, manufactured by Nippon Food Processing Co., Ltd.) was added to 100 parts by weight of the resulting oligomer oligomer containing polyester as the main component, and the mixture was heated at 180 ° C. for 5 days. After kneading for 1 minute, 6 parts by weight of 1,4-butanediol and 4,4 '
-Adding 105 parts by weight of diphenylmethane diisocyanate and using a Brabender Plastograph extruder, 1
The mixture was kneaded at 80 ° C. for 5 minutes, 0.3 part by weight of calcium stearate was further added and kneaded for 1 minute, and then extruded to obtain a resin composition. The obtained resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1. In addition,
Since it was not possible to obtain a uniform test piece, the tensile strength at break and tensile elongation at break were not evaluated.

[0095]

[Table 1]

Example 8 190 parts by weight of adipic acid, 14,4-butanediol 14
0 parts by weight, 162 parts by weight of 2,2-dimethyl-1,3-propanediol (dicarboxylic acid component at the time of preparation / diol component = 1 / 2.4 (molar ratio)), 6-nylon manufactured by Toyobo Co., Ltd. (T850 , 98% sulfuric acid, reduced viscosity at 20 ° C .: 3.5 dL / g) 628 parts by weight, tetrabutoxy titanium 0.4 part by weight as a catalyst, 1,3,5-trimethyl-2,4,6- 0.4 parts by weight of tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene,
0.4 parts by weight of tris (2,4-di-t-butylphenyl) phosphite was added, and the reaction system was heated to 200 ° C. under nitrogen. After 10 minutes, the nylon dissolved and became a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of esterification reaction, 2
The temperature was raised to 240 ° C. in 0 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 1 mmHg or less in 10 minutes. In this state, polycondensation reaction was performed for 60 minutes to obtain 897 parts by weight of polyesteramide.

The intrinsic viscosity of the obtained polyesteramide was measured in the same manner as in Example 1. As a result, [η] = 0.9
It was 5 dL / g. Polyesteramide 10 obtained
300 parts by weight of corn starch (PA # 220, average particle size 15 μm, manufactured by Nippon Food Processing Co., Ltd.) was added to 0 parts by weight, and 2 parts were added using a Brabender Plastograph extruder.
The mixture was kneaded at 05 ° C. for 10 minutes and extruded to obtain a resin composition. The resin composition thus obtained was injection molded (injection pressure 1500 kgf / cm ² , mold temperature 70 ° C., cylinder temperature 215 ° C.) into a No. 3 dumbbell test piece, and the physical properties of the obtained test piece were measured by the following methods. It was evaluated by. The results are shown in Table 2.

Evaluation method 1. Tensile Breaking Strength and Tensile Breaking Elongation Measured at room temperature (23 ° C.) according to JIS K 6301. 2. Polyamide content in polyester amide It was calculated from the weight of polyamide when charged with respect to the weight of polyester produced. 3. Evaluation of biodegradability Based on JIS K 6950, the degree of biodegradation after 28 days in a room temperature (23 ° C) environment was measured by the BOD value.

Example 9 Example 9 was repeated except that 97 parts by weight of ethylene glycol and 119 parts by weight of propylene glycol were used as diol components, the amount of 6-nylon added was 26 parts by weight, and the polycondensation reaction time was 90 minutes. In the same manner as in Example 8, 466 parts by weight of polyesteramide was obtained.

The intrinsic viscosity of the obtained polyesteramide was measured in the same manner as in Example 1. As a result, [η] = 1.1
dL / g. Polyesteramide 100 obtained
400 parts by weight of corn starch (PA # 220, average particle size 15 μm, manufactured by Nippon Food Processing Co., Ltd.) was added to 18 parts by weight using a Brabender Plastograph extruder.
The mixture was kneaded at 0 ° C. for 10 minutes and extruded to obtain a resin composition.
The obtained resin composition is injection molded (injection pressure 1
500 kgf / cm ² , mold temperature 70 ° C., cylinder temperature 200 ° C.), a No. 3 dumbbell test piece was prepared and evaluated in the same manner as in Example 8. The results are shown in Table 2.

Example 10 Except that 97 parts by weight of ethylene glycol and 162 parts by weight of 2,2-dimethyl-1,3-propanediol were used as diol components, and the addition amount of 6-nylon was 251 parts by weight. 502 parts by weight of polyesteramide were obtained in the same manner as in Example 8.

The intrinsic viscosity of the obtained polyesteramide was measured in the same manner as in Example 1. As a result, [η] = 1.0
dL / g. Polyesteramide 100 obtained
850 parts by weight of corn starch (PA # 220, average particle size 15 μm, manufactured by Nippon Food Processing Co., Ltd.) was added to 20 parts by weight, and 20 parts were added using a Brabender Plastograph extruder.
The mixture was kneaded at 0 ° C. for 10 minutes and extruded to obtain a resin composition.
The obtained resin composition is injection molded (injection pressure 1
500 kgf / cm ² , mold temperature 70 ° C., cylinder temperature 210 ° C.), a No. 3 dumbbell test piece was prepared and evaluated in the same manner as in Example 8. The results are shown in Table 2.

Example 11 A test piece was prepared and evaluated in the same manner as in Example 10 except that the amount of corn starch added was 60 parts by weight. The results are shown in Table 2.

Example 12 A test piece was prepared and evaluated in the same manner as in Example 9 except that the amount of corn starch added was 800 parts by weight.
The results are shown in Table 2.

Comparative Example 4 Example 8 except that no corn starch was added.
Test pieces were prepared and evaluated in the same manner as in. The results are shown in Table 2.

Comparative Example 5 Example 9 except that no corn starch was added.
Test pieces were prepared and evaluated in the same manner as in. The results are shown in Table 2.

Comparative Example 6 An attempt was made to prepare a test piece in the same manner as in Example 10 except that the amount of corn starch added was 950 parts by weight, but a molding material of uniform material could not be obtained. Therefore, the tensile breaking strength and tensile elongation were not evaluated.

Comparative Example 7 A test piece was prepared and evaluated in the same manner as in Example 11 except that the amount of corn starch added was 40 parts by weight. The results are shown in Table 2.

Comparative Example 8 An attempt was made to prepare a test piece in the same manner as in Example 12 except that biodegradable resin Bionore # 3000 (manufactured by Showa Highpolymer Co., Ltd.) was used instead of polyesteramide. Since it was not possible to obtain a molding material having a uniform material, the tensile breaking strength and the tensile elongation were not evaluated.

[0110]

[Table 2]

[0111]

Since the resin composition of the present invention has the above-mentioned constitution, it has mechanical properties such as tensile breaking strength and tensile breaking elongation and biodegradability in a temperature range from room temperature to practically high temperature. Is excellent.

Claims (4)

[Claims] 1. An intrinsic viscosity (in o-chlorophenol, 30 ° C.) of which the main component is polyester is 0.1 to 0.9.
It is obtained by mixing 50 to 900 parts by weight of biodegradable organic fine particles with 100 parts by weight of an oligomer of dL / g, and then adding 1 to 100 parts by weight of a polyfunctional isocyanate compound and reacting them. A characteristic resin composition. 2. An intrinsic viscosity (in o-chlorophenol, 30 ° C.) of which the main component is polyester is 0.1 to 0.9.
The oligomer of dL / g has the general formula (1) HOOC-R ¹ -COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms).
At least one kind of dicarboxylic acids represented by the following general formula (2) HO—R ² —OH (2) (in the formula, R ² represents an alkylene group having 2 to 6 carbon atoms).
At least one of the diols represented by and reduced viscosity (1 g / dL 98% sulfuric acid solution, 20 ° C.) is 0.5
The resin composition according to claim 1, wherein the resin composition comprises a polyamide having a content of ˜7 dL / g, and the content of the polyamide is 3 to 50% by weight. 3. General formula (3) HOOC—R ³ —COOH (3) (wherein R ³ represents an alkylene group having 2 to 8 carbon atoms).
And at least one of the dicarboxylic acids represented by the general formula (4) HO—R ⁴ —OH (4) (wherein R ⁴ represents an alkylene group having 2 to 6 carbon atoms).
To 100 parts by weight of the polyester constituent component consisting of at least one of the diols represented by
dL98% sulfuric acid solution, 20 ° C.) 0.5 to 7 dL / g of polyamide 3 to 250 parts by weight is dissolved, and the esterification reaction of the polyester constituent is conducted at 150 to 230 ° C.
After that, 100 parts by weight of polyesteramide obtained by polymerization at 180 to 260 ° C. under reduced pressure is mixed with 50 to 900 parts by weight of biodegradable organic fine particles. A characteristic resin composition. 4. The resin composition according to claim 1, 2 or 3, wherein the biodegradable organic fine particles are starch.