JPH08239572A - Polyurethane resin composition - Google Patents

Abstract

PURPOSE: To obtain a polyurethane resin composition greatly improved in injection moldability in spite of a low hardness, having a small compressive permanent strain in its molded product and excellent in various characteristics such as strength, heat resistance, cold resistance, etc. CONSTITUTION: This polyurethane resin composition is obtained by blending 100 pts.wt. specific polyurethane described below and having <=80 hardness with 5-20 pts.wt. thermoplastic graft copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyanide compound to an elastomer. The specific polyurethane is obtained by reacting a high molecular diol [(a) mole] having 3000-7000 number average molecular weight and comprising a diol unit consisting of 100-30 mole 3-methyl-1,5-pentanediol (MPD) unit and 0-70 mole 1,9-nonanediol (ND) unit, a dicarboxylic acid unit of the formula; CO-(CH2 )n -CO [(n) is 4-10] with an organic diisocyanate [(b) mole] and a chain elongation agent [(c) mole] in a ratio satisfying the equation; 1.02<=b/(a+c)<=1.08.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane composition obtained by blending an incomplete thermoplastic polyurethane having a low hardness with a specific thermoplastic graft polymer. INDUSTRIAL APPLICABILITY The polyurethane composition of the present invention is not only excellent in various properties such as strength, compression set, heat resistance and cold resistance, but also significantly improved in injection moldability, so that it is useful as a material for various molded products. Is.

[0002]

2. Description of the Related Art Polyurethane has many features such as high elasticity, excellent abrasion resistance and oil resistance, and is therefore attracting attention as a substitute material for rubber and plastics, and ordinary plastics molding processing methods can be applied. As a molding material, it has come to be used in a wide range of applications.

[0003]

However, the conventional low-hardness polyurethane has insufficient properties such as strength, compression set, heat resistance, and cold resistance, and is also inferior in moldability. Among these low hardness polyurethanes, in the case of incomplete thermoplastic polyurethane (polyurethane produced using an excess amount of organic diisocyanate with respect to the total number of moles of polymer diol and chain extender), strength and compression Although the permanent set and heat resistance are relatively improved, the adhesiveness with metal is extremely high, so that the mold is not properly released from the mold during injection molding, and the resin flows unevenly in the mold. Defects (air bubbles and flow patterns) on the surface of the molded product are likely to occur. In order to further promote rubber substitution with low-hardness polyurethane, it is essential to improve various performances and improve moldability in particular.

An object of the present invention is to provide a low hardness polyurethane composition which is not only excellent in various properties such as strength, compression set, heat resistance and cold resistance, but also has remarkably improved injection moldability. It is in.

[0005]

According to the present invention, the above object consists of [A] 3-methyl-1,5-pentanediol units and 1,9-nonanediol units, and 3-methyl- 1,5-Pentanediol unit and 1,9-
The molar ratio of nonanediol units is 70:30 to 30:70.
And a dicarboxylic acid unit represented by the following general formula (I): —CO— (CH ₂ ) n—CO— (I) (wherein n represents an integer of 4 to 10). Number average molecular weight of 3,000 to 7,000
Polymer diol (a), organic diisocyanate (b)
And the chain extender (c) are represented by the following formula (i); 1.02 ≦ b / (a + c) ≦ 1.08 (i) (wherein, a is the number of moles of the polymer diol, and b is the organic diisocyanate). The hardness (JIS-A) obtained by reacting at a ratio satisfying the number of moles, and c is the number of moles of the chain extender.
A polyurethane composition obtained by blending 5 to 20 parts by weight of a thermoplastic graft polymer obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyanide compound to an elastomer [B] to 100 parts by weight of a polyurethane having a ratio of 80 or less. It is achieved by

The polymeric diol constituting the polyurethane used in the present invention is substantially composed of diol units and dicarboxylic acid units. The diol unit is
3-methyl-1,5-pentanediol unit and 1,
Consisting of 9-nonanediol units and 3-methyl-
The molar ratio of the 1,5-pentanediol unit and the 1,9-nonanediol unit is 70:30 to 30:70, and 6
It is preferably 0:40 to 30:70. When the molar ratio of the 3-methyl-1,5-pentanediol unit and the 1,9-nonanediol unit is 70:30 to 30:70, the resulting polyurethane composition has a compression set, heat resistance and cold resistance. Will be good. As a diol unit, a 3-methyl-1,5-pentanediol unit and a 1,9-nonanediol unit are included, and if necessary, a small amount (usually 20 mol% or less of all diol units) of other diol units are contained. You may stay. For example, ethylene glycol, diethylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,6-
Mention may be made of units derived from diols such as hexanediol, neopentyl glycol, 2-methyl-1,8-octanediol.

The dicarboxylic acid unit may be any of aliphatic dicarboxylic acid units in which n is an integer of 4 to 10 in the above general formula (I), and one or more of these units may be contained. it can. These aliphatic dicarboxylic acid units are derived from, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like. Among these, aliphatic dicarboxylic acid units having n of 4 to 8 in the above general formula (I) derived from adipic acid, azelaic acid, sebacic acid and the like are preferable. As a dicarboxylic acid unit, together with these aliphatic dicarboxylic acid units, a small amount (usually,
It may contain units derived from aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid in an amount of 20 mol% or less of all dicarboxylic acid units.

The number average molecular weight of the polymeric diol is 3000
˜7,000, preferably 3,000 to 6,000. When the number average molecular weight of the high molecular diol is less than 3000, the heat resistance, compression set and moldability of the obtained polyurethane composition are deteriorated. On the other hand, when the number average molecular weight of the high molecular weight diol exceeds 7,000, the productivity of the polyurethane composition decreases and the resulting polyurethane composition has poor mechanical strength and the like. In addition,
The number average molecular weight of the polymer diols referred to in the present specification is a number average molecular weight calculated based on a hydroxyl value measured according to JIS K 1577.

The above-mentioned polymer diol is produced by polycondensing the above-mentioned dicarboxylic acid component and diol component by a conventionally known transesterification reaction, direct esterification reaction or the like. In that case, the polycondensation reaction can be carried out in the presence of a titanium-based or tin-based polycondensation catalyst, but when a titanium-based polycondensation catalyst is used,
After the completion of the polycondensation reaction, it is preferable to deactivate the titanium-based polycondensation catalyst contained in the polymer diol.

When a titanium-based polycondensation catalyst is used in the production of the polymeric diol, any titanium-based polycondensation catalyst conventionally used in the production of polyester diols can be used, and there is no particular limitation. Examples of the polycondensation catalyst include titanic acid, tetraalkoxytitanium compounds, titanium acylate compounds, and titanium chelate compounds. More specifically, tetraalkoxytitanium compounds such as tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2-ethylhexyl titanate and tetrastearyl titanate, polyhydroxytitanium stearate,
Examples thereof include titanium acylate compounds such as polyisopropoxy titanium stearate, titanium acetyl acetate, triethanolamine titanate, titanium ammonium lactate, titanium ethyl lactate, and titanium chelate compounds such as titanium octylene glycolate.

The amount of the titanium-based polycondensation catalyst used can be appropriately adjusted according to the intended polymer diol and the content of the polyurethane produced using the same, and is not particularly limited, but generally, the polymer diol is used. About 0.1 to 50 ppm, based on the total weight of the reaction components to form
Is preferred and about 1 to 30 ppm is more preferred.

The titanium polycondensation catalyst contained in the polymer diol can be deactivated by, for example, bringing the polymer diol obtained by the completion of the esterification reaction into contact with water under heating to deactivate it. Examples thereof include a method in which the polymer diol is treated with a phosphorus compound such as phosphoric acid, phosphoric acid ester, phosphorous acid, and phosphorous acid ester. When deactivating the titanium-based polycondensation catalyst by contacting with water, 1% by weight or more of water is added to the polyester diol obtained by the esterification reaction, and the temperature is 70 to 150 ° C., preferably 90 to 1
It is advisable to heat at a temperature of 30 ° C for 1 to 3 hours. The deactivation treatment of the titanium-based polycondensation catalyst may be performed under normal pressure or under pressure. It is desirable to depressurize the system after deactivating the titanium-based polycondensation catalyst because the water used for deactivation can be removed.

The type of organic diisocyanate used in the production of polyurethane is not particularly limited, and any organic diisocyanate conventionally used in the production of ordinary polyurethane can be used, and those having a molecular weight of 500 or less are preferable. Examples of organic diisocyanates include:
For example, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, toluylene diisocyanate, 1,5-naphthylene diisocyanate,
Aromatic diisocyanates such as 3,3′-dichloro-4,4′-diphenylmethane diisocyanate, xylylene diisocyanate and toluylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylylene Examples thereof include aliphatic or alicyclic diisocyanates such as diisocyanate. Of these organic diisocyanates,
One type or two or more types are used. Among these,
Preference is given to using 4,4′-diphenylmethane diisocyanate.

As the chain extender used in the production of polyurethane, any of those conventionally used in the production of ordinary polyurethane can be used, and it is not particularly limited, but an active hydrogen atom capable of reacting with an isocyanate group in the molecule is used. To 2
It is preferable to use a low molecular weight compound having a molecular weight of 400 or less having one or more. For example, ethylene glycol, 1,
4-butanediol, 1,6-hexanediol, 1,
9-nonanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol,
Diols such as bis (β-hydroxyethyl) terephthalate and p-xylylene glycol, hydrazine,
Diamines such as ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, piperazine derivatives, phenylenediamine, tolylenediamine, xylenediamine, adipic acid dihydrazide, isophthalic acid dihydrazide, aminoethyl alcohol, aminopropyl alcohol, ethanolamine, etc. Amino alcohols, etc.
One kind or two or more kinds are used. Among these,
Particular preference is given to using 1,4-butanediol.

In the production of polyurethane, the above-mentioned polymer diol, organic diisocyanate and chain extender are added to the following formula (i); 1.02≤b / (a + c) ≤1.08 (i) (wherein a is the number of moles of the polymeric diol, b is the number of moles of the organic diisocyanate, and c is the number of moles of the chain extender). b / (a + c)
If the value is less than 1.02, the compression molding strain of the obtained polyurethane composition is large and the performance such as heat resistance is deteriorated, which is not preferable. On the other hand, the value of b / (a + c) is 1.0
When it exceeds 8, it becomes difficult to pelletize polyurethane during production, or sticking between pellets easily occurs. Furthermore, since the obtained polyurethane composition has a high adhesiveness with a metal, it is not preferable because it has a poor releasability from the mold when injection molding and the appearance of the molded product is extremely poor.

In producing a polyurethane using the above-mentioned polymer diol, organic diisocyanate and chain extender, it is preferable to use a tin-based urethane-forming catalyst having catalytic activity for the urethane-forming reaction. When the tin-based urethane-forming catalyst is used, the molecular weight of the polyurethane increases rapidly, and the molecular weight of the polyurethane is maintained at a sufficiently high level even after molding, so that a polyurethane composition having better various physical properties can be obtained. The amount of the tin-based urethane-forming catalyst used is 0.5 to 10 in terms of tin atom based on polyurethane (that is, the total weight of the reactive raw material compounds such as polymer diol, organic diisocyanate and chain extender used for producing polyurethane). It is preferably 15 ppm. If the amount of the tin-based urethane-forming catalyst used is more than 15 ppm in terms of tin atom based on polyurethane, performance such as hydrolysis resistance and thermal stability deteriorates, which is not preferable.

Examples of the tin-based urethane-forming catalyst include:
Tin octylate, monomethyltin mercaptoacetate, monobutyltin triacetate, monobutyltin monooctylate, monobutyltin monoacetate, monobutyltin maleate, monobutyltin maleate benzyl ester salt, monooctyltin maleate, monooctyltin thiol Dipropionate, monooctyltin tris (isooctylthioglycolate), monophenyltin triacetate, dimethyltin maleate ester, dimethyltin bis (ethylene glycol monothioglycolate), dimethyltin bis (mercaptoacetic acid) salt , Dimethyltin bis (3-mercaptopropionic acid) salt, dimethyltin bis (isooctyl mercaptoacetate), dimethyltin diacetate, dibutyltin diacetate, di Chilltin dioctoate, dibutyltin distearate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin maleate ester salt, dibutyltin bis (mercaptoacetic acid) salt, dibutyltin bis (mercaptoacetic acid alkyl ester) salt, dibutyltin bis (3
-Mercaptopropionic acid alkoxybutyl ester)
Salt, dibutyltin bisoctyl thioglycol ester salt, dibutyltin (3-methicaptopropionic acid) salt,
Dioctyl tin maleate, dioctyl tin maleate salt, dioctyl tin maleate polymer,
Dioctyl tin dilaurate, dioctyl tin bis (isooctyl mercaptoacetate), dioctyl tin bis (isooctyl thioglycolic acid ester), dioctyl tin bis (3-mercaptopropionic acid) salt, and the like, and one or two of them are listed. The above is used. Among these, dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin bis (3-mercaptopropionic acid alkoxybutyl ester) salts are preferable.

The method for producing the polyurethane is not particularly limited, and by using the above-mentioned polymer diol, organic diisocyanate and chain extender and utilizing the well-known urethanization reaction technique, either the prepolymer method or the one-shot method. It may be manufactured. Among them, it is preferable to carry out melt polymerization in the substantial absence of a solvent, and particularly preferable is continuous melt polymerization using a multi-screw extruder.

The polyurethane used in the present invention is a low hardness polyurethane having a hardness (JIS-A) of 80 or less. Use of a polyurethane having a hardness of more than 80 is not preferable because the flexibility of the obtained polyurethane composition is lowered. Small compression set, heat resistance,
The hardness is 55 to 8 from the viewpoint that a polyurethane composition having excellent performance such as cold resistance and improved injection moldability can be obtained.
Preference is given to using polyurethanes in the range 0.

The logarithmic viscosity of the polyurethane used in the present invention is obtained by dissolving polyurethane in a solution of N, N-dimethylformamide containing 0.05 mol / l of n-butylamine to a concentration of 0.5 g / dl. When measured at 30 ° C., it is preferably 0.5 to 2.0 dl / g, and more preferably 0.9 to 2.0 dl / g. It is preferable to use a polyurethane having a logarithmic viscosity in the range of 0.5 to 2.0 dl / g because a polyurethane composition having a small compression set and good mechanical performance and heat resistance can be obtained.

The polyurethane composition of the present invention comprises 100 parts by weight of the above polyurethane and 5 to 20 parts by weight of a thermoplastic graft polymer obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyanide compound on an elastomer. It is necessary to add 5 to 15 parts by weight, more preferably 10 to 15 parts by weight. When the blending amount of this thermoplastic graft polymer is less than 5 parts by weight, the resulting polyurethane composition has a high adhesiveness with a metal, and has poor mold releasability from a mold when injection-moldable, resulting in molding. This is not preferable because the appearance of the product tends to be inferior. On the other hand, when the compounding amount of these compounds exceeds 20 parts by weight, various physical properties such as flexibility, mechanical strength, abrasion resistance and compression set of the obtained polyurethane composition tend to be deteriorated, which is preferable. Absent.

As the elastomer serving as a graft substrate for the above-mentioned thermoplastic graft polymer, those having a second-order transition temperature lower than -30 ° C are preferable. Further, examples of the aromatic vinyl compound which is one of the graft monomers include styrene, α-methylstyrene, alkyl-substituted styrene, halogen-substituted styrene and the like, and among these, styrene is particularly preferable. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is particularly preferable.

As the thermoplastic graft polymer, for example, a copolymer obtained by adding both graft monomers of acrylonitrile and styrene to a latex of a butadiene-based polymer and emulsion-polymerizing it, an acrylonitrile-butadiene copolymer and a styrene-acrylonitrile copolymer. Examples thereof include blended polymers obtained by blending with a polymer (hereinafter referred to as ABS resin). As the butadiene-based polymer latex, polybutadiene latex, acrylonitrile-butadiene copolymer latex, styrene-butadiene copolymer latex and the like are used. The proportion of each of the above components in the ABS resin is generally 5 to 50% by weight of butadiene and 20% of styrene.
˜85 wt%, acrylonitrile 5˜40 wt%.

Another example of the thermoplastic graft polymer is a resin obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyanide compound on ethylene-propylene rubber (hereinafter referred to as AES resin). Can be mentioned. As the ethylene-propylene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-
Diene copolymer rubber or the like is used. The weight ratio of ethylene and propylene (ethylene: propylene) is 9: 1 to 2:
A range of 8 is preferred. Further, as the diene monomer,
Norbornenes such as alkenyl norbornene, cyclic dienes such as dicyclopentadiene, and aliphatic dienes such as hexadiene are used. The diene monomer is used alone or in combination of two or more. Weight ratio of ethylene-propylene rubber and graft monomer such as aromatic vinyl compound and vinyl cyanide compound (ethylene-propylene rubber: graft monomer)
In general, the range of 5:95 to 50:50 is suitable, and the range of 10:90 to 40:60 is preferable. AES
The resin is produced by a bulk polymerization method, an emulsion polymerization method, a solution polymerization method, a bulk-suspension polymerization method, or the like.

The polyurethane composition of the present invention can be produced using the above-mentioned polyurethane and thermoplastic graft polymer by a conventional polymer blending technique. For example, polyurethane and a thermoplastic graft polymer are pre-mixed at a predetermined ratio using a vertical or horizontal mixer that is usually used for mixing resin materials, and then a single-screw or twin-screw extruder is used. It is produced by melt-kneading under heating in a batch system or a continuous system using a mixing roll, a Banbury mixer or the like. When mixing, in addition to the above-mentioned thermoplastic graft polymer, additives such as an ultraviolet absorber, an antioxidant, a plasticizer, an antistatic agent, and a hydrolysis inhibitor may be added, if necessary.

The polyurethane composition of the present invention can be hot-melt molded and heat-processed, and various molded products can be smoothly processed by any molding method such as extrusion molding, injection molding, blow molding, calender molding and casting. It can be manufactured. Among these molding methods, it is particularly suitable as a material for injection molding.

A molded article obtained by using the polyurethane composition of the present invention has a low hardness and a small compression set and is excellent in various properties such as strength, heat resistance and cold resistance. , Belts, hoses, tubes,
It is useful as a material for various applications such as automobile parts, machine parts, shoe soles, watch bands, packing materials, and vibration damping materials.

As the molded product made of the polyurethane composition of the present invention, the molded product may be used as it is, but the molded product is heat-treated (annealed) at a temperature of 60 ° C. or higher, particularly in a range of 70 to 110 ° C. In this case, the compression set is smaller and the heat resistance is more excellent, which is preferable. The heat treatment time of the molded product can be appropriately selected according to the type of the polyurethane composition, the shape of the molded product, the heat treatment temperature, etc., but it is usually preferably about 2 to 24 hours.

[0029]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following Examples, Comparative Examples and Reference Examples, the number average molecular weight of the polymeric diol; the hardness and logarithmic viscosity of polyurethane; the strength, compression set, heat resistance and cold resistance of molded articles obtained from the polyurethane composition; The moldability of the polyurethane composition was measured or evaluated by the following method.

[Number average molecular weight of polymer diol] JIS
It was calculated from the hydroxyl value of the polymeric diol measured according to K 1577.

[Hardness] Shore hardness A was determined according to JIS K 6301 using two disc-shaped products (diameter 120 mm, thickness 2 mm) obtained by injection molding.

[Logarithmic viscosity] 0.05% of n-butylamine
Polyurethane was dissolved in a N / N-dimethylformamide solution containing 1 mol / l to a concentration of 0.5 g / dl, and the flow time of the polyurethane solution at 30 ° C. was measured using an Ubbelohde viscometer. The logarithmic viscosity was determined by the following formula.

Logarithmic viscosity = {ln (t / t ₀ )} / c [where t is the flow-down time (seconds) of the polyurethane solution, t
₀ represents the flow time of the solvent (seconds), and c represents the concentration of the polyurethane solution (g / dl). ]

[Strength] A disc-shaped product (diameter 120 mm, thickness 2 mm) obtained by injection molding was used to make a punching test piece with dumbbell No. 3, and the test piece was measured according to JIS K 7311.

[Compression Molding Strain] Using a test piece having a thickness of 2 mm obtained by injection molding, a test was conducted by a method according to JIS K 6301 (compressibility of the test piece: 25%, heat treatment at 70 ° C. for 22 hours). went.

[Heat Resistance] A thickness of 2 mm obtained by injection molding using DVE Rheo Spectra manufactured by Rheology Co., Ltd.
The dynamic viscoelasticity of the test piece prepared from the disk-shaped material of
The temperature was measured at 1 Hz, and the end point temperature on the high temperature side of the rubber-like flat area of the dynamic storage elastic modulus E'was used as an index of heat resistance.

[Cold resistance] A thickness of 2 mm obtained by injection molding using DVE Rheo Spectra manufactured by Rheology Co., Ltd.
The dynamic viscoelasticity of the test piece prepared from the disk-shaped material of
It was measured at 1 Hz, and the cold resistance was evaluated by the temperature (Tα) at which the dynamic loss elastic modulus E ″ peaks.

[Moldability] A disk-shaped material (diameter 120 mm, thickness 2 mm) is injection-molded (cylinder temperature: 170 to 200 ° C., mold temperature: 30 ° C.) using a mold having a mirror-finished surface. At the time of molding, the mold release state of the molded article from the mold and the surface state of the molded article were observed, and the moldability was evaluated according to the following criteria. ◯: The molded product is easily released from the mold, and the surface of the molded product is smooth. X: The adhesion between the molded product and the mold is high, and the surface of the molded product is slightly deformed. XX: The adhesion between the molded product and the mold is remarkably high, and unevenness is generated on the surface of the molded product.

Abbreviations and compound names relating to the compounds used in Tables 2 and 3 below are shown in Table 1 below.

[0040]

[Table 1]

Reference Example 1 3980 g of 3-methyl-1,5-pentanediol,
4,204 g of 1,9-nonanediol and 7 of adipic acid
300 g was charged into the reactor, and the esterification reaction was carried out under normal pressure while distilling off the water produced at 200 ° C. to the outside of the system. When the acid value of the reaction product became 30 or less, 90 mg of tetraisopropyl titanate was added, and 200-100 mmH
The reaction was continued while reducing the pressure to g. When the acid value reached 1.0, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction, and 12800 g of a polymer diol was obtained. The obtained polymer diol is heated to 100 ° C., 3% by weight of water is added thereto, and the mixture is stirred and heated for 2 hours to deactivate the titanium-based catalyst, and then water is distilled off under reduced pressure. By
A polymer diol (hereinafter referred to as PNMA-A) in which the titanium-based polycondensation catalyst was deactivated was obtained. PNMA-A
The structural unit and number average molecular weight of are shown in Table 2 below.

Reference Example 2 3-methyl-1,5-pentanediol 3356 g,
4,908 g of 1,9-nonanediol and 7 of adipic acid
An esterification reaction was carried out in the same manner as in Reference Example 1 except that 300 g was used to obtain 12590 g of a high molecular diol.
Further, a polymer diol (hereinafter referred to as PNMA-B) in which the titanium-based polycondensation catalyst was deactivated was obtained in the same manner as in Reference Example 1. The structural unit and number average molecular weight of PNMA-B are shown in Table 2 below.

Reference Example 3 3-methyl-1,5-pentanediol 1920 g,
1416 g of 1,9-nonanediol and adipic acid 2
An esterification reaction was carried out in the same manner as in Reference Example 1 except that 920 g was used to obtain 5090 g of a polymer diol. Further, a polymer diol (hereinafter referred to as PNMA-C) in which the titanium-based polycondensation catalyst was deactivated was obtained in the same manner as in Reference Example 1. The structural unit and number average molecular weight of PNMA-C are shown in Table 2 below.

Reference Example 4 3-methyl-1,5-pentanediol 3747 g,
4,520 g of 1,9-nonanediol and adipic acid 7
The esterification reaction was performed in the same manner as in Reference Example 1 except that 300 g was used to obtain 13350 g of a high molecular diol.
Further, a polymer diol (hereinafter referred to as PNMA-D) in which the titanium-based polycondensation catalyst was deactivated was obtained in the same manner as in Reference Example 1. The structural unit and number average molecular weight of PNMA-D are shown in Table 2 below.

Reference Example 5 Polymeric diol 116 was subjected to the esterification reaction in the same manner as in Reference Example 1 except that 7080 g of 3-methyl-1,5-pentanediol and 7300 g of adipic acid were used.
70 g were obtained. Further, a polymer diol (hereinafter referred to as PMPA-A) in which the titanium-based polycondensation catalyst was deactivated was obtained in the same manner as in Reference Example 1. The structural unit and number average molecular weight of PMPA-A are shown in Table 2 below.

Reference Example 6 7870 g of 1,9-nonanediol and 5 adipic acid
The esterification reaction was carried out in the same manner as in Reference Example 1 except that 840 g was used to obtain 11500 g of a high molecular diol.
Further, a polymer diol (hereinafter referred to as PNA-A) in which the titanium-based polycondensation catalyst was deactivated was obtained in the same manner as in Reference Example 1. The structural unit and number average molecular weight of PNA-A are shown in Table 2 below.

Reference Example 7 5,400 g of 1,4-butanediol and adipic acid 7
An esterification reaction was carried out in the same manner as in Reference Example 1 except that 300 g was used to obtain 10180 g of a high molecular diol.
Further, a polymer diol in which the titanium-based polycondensation catalyst was deactivated (hereinafter referred to as PBA-A) was obtained in the same manner as in Reference Example 1. The structural unit and number average molecular weight of PBA-A are shown in Table 2 below.

[0048]

[Table 2]

Example 1 PNMA-A obtained in Reference Example 1 was supplemented with 11.9 ppm of dibutyltin acetate as a tin-based urethane-forming catalyst.
(4.4 ppm in terms of tin atom) was added. The tin-based urethane-forming catalyst-containing PNMA-A, 1,4-butanediol, and 4,4′-diphenylmethane diisocyanate heated and melted at 50 ° C. were mixed with the tin-based urethane-forming catalyst-containing PNMA-A: 1,4-butanediol: 4,4'-
The molar ratio of diphenylmethane diisocyanate is 1: 3.
The ratio is 0: 4.12, and the total amount of these is 300.
A twin-screw extruder (30 mmφ, L / D = rotating coaxially with a metering pump so as to achieve g / min)
36, cylinder temperature: 75 to 260 ° C.) to continuously carry out continuous melt polymerization. The resulting polyurethane melt is continuously extruded into water in strands and then cut into pellets with a pelletizer, which pellets are
By dehumidifying and drying at 20 ° C. for 20 hours, a polyurethane having hardness and logarithmic viscosity shown in Table 3 below was obtained. 100 parts by weight of the obtained polyurethane and 10 parts by weight of AES resin (JSR-AES110 manufactured by Japan Synthetic Rubber Co., Ltd.) were mixed with a single screw extruder (25 mmφ, cylinder temperature: 170).
After melting and kneading at ˜200 ° C., die temperature: 190 ° C.), the mixture was pelletized and the pellets were dehumidified and dried at 80 ° C. for 2 hours or more. Using the dried pellets, the moldability of the polyurethane composition was evaluated by the above method. Furthermore, a disk-shaped product (diameter 120 mm, thickness 2 mm) obtained by injection molding (cylinder temperature: 170 to 200 ° C., mold temperature: 30 ° C.) using this dried pellet was
After heat treatment at 8 ° C. for 8 hours, the strength, compression set, heat resistance and cold resistance were evaluated by the above methods. The results are shown in Table 4 below.

Example 2 In Example 1, the tin-based urethane-forming catalyst-containing PNMA was used.
The molar ratio of -A: 1,4-butanediol: 4,4'-diphenylmethane diisocyanate is 1: 3.0: 4.2.
A continuous melt polymerization reaction was performed in the same manner except that it was 0 to obtain a polyurethane having hardness and logarithmic viscosity shown in Table 3 below. Further, using the obtained polyurethane, a polyurethane composition was prepared in the same manner as in Example 1, and the moldability, strength, compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

Example 3 A continuous melt polymerization reaction was performed in the same manner as in Example 1 except that the PNMA-B obtained in Reference Example 2 was used to obtain a polyurethane having hardness and logarithmic viscosity shown in Table 3 below. Obtained. Furthermore, using the obtained polyurethane, Example 1
A polyurethane composition was prepared in the same manner as above, and the moldability, strength, compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

Example 4 A polyurethane having the hardness and the logarithmic viscosity shown in Table 3 below was obtained in the same manner as in Example 1. Further, a polyurethane composition was prepared in the same manner as in Example 1 except that 10 parts by weight of ABS resin (JSR-ABS12 manufactured by Nippon Synthetic Rubber Co., Ltd.) was used with respect to 100 parts by weight of the obtained polyurethane. The moldability, strength, compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

Example 5 In Example 1, using the PNMA-C obtained in Reference Example 3, the tin-based urethane-containing catalyst-containing PNMA-C: 1,
A continuous melt polymerization reaction was performed in the same manner as in Example 1 except that the molar ratio of 4-butanediol: 4,4′-diphenylmethane diisocyanate was 1: 2.0: 3.12,
A polyurethane having hardness and logarithmic viscosity shown in Table 3 below was obtained. Furthermore, using the obtained polyurethane,
A polyurethane composition was prepared in the same manner as in Example 1 and evaluated for moldability, strength, compression set, heat resistance and cold resistance. The results are shown in Table 4 below.

Example 6 A polyurethane having the hardness and the logarithmic viscosity shown in Table 3 below was obtained in the same manner as in Example 1. Furthermore, with respect to 100 parts by weight of the obtained polyurethane, 5 parts by weight of AES resin (manufactured by Japan Synthetic Rubber Co., Ltd., JSR-AES110) and ABS resin (manufactured by Japan Synthetic Rubber Co., Ltd., JSR-ABS).
12) A polyurethane composition was prepared in the same manner as in Example 1 except that 5 parts by weight was used, and moldability, strength, compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

Comparative Example 1 A polyurethane having the hardness and the logarithmic viscosity shown in Table 3 below was obtained in the same manner as in Example 1. Moldability, strength, compression set, heat resistance and cold resistance were evaluated in the same manner as in Example 1 without adding a thermoplastic graft polymer to the obtained polyurethane. The results are shown in Table 4 below.

Comparative Example 2 In Example 1, the PNMA-D obtained in Reference Example 4 was used, and the tin-based urethane-containing catalyst-containing PNMA-D: 1, 1.
A continuous melt polymerization reaction was performed in the same manner except that the molar ratio of 4-butanediol: 4,4′-diphenylmethane diisocyanate was 1: 1.1: 2.16, and the hardness and logarithmic viscosity shown in Table 3 below were obtained. A polyurethane having was obtained.
Further, using the obtained polyurethane, a polyurethane composition was prepared in the same manner as in Example 1 to obtain moldability, strength,
The compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

Comparative Example 3 In Example 1, the PNA-A obtained in Reference Example 6 was used, and the tin-based urethane-containing catalyst-containing PNA-A: 1,4-
A polyurethane having the hardness and logarithmic viscosity shown in Table 3 below was carried out in the same manner except that the molar ratio of butanediol: 4,4′-diphenylmethane diisocyanate was 1: 2.0: 3.09. Got Further, using the obtained polyurethane, a polyurethane composition was prepared in the same manner as in Example 1, and the moldability, strength, compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

Comparative Example 4 A continuous melt polymerization reaction was carried out in the same manner as in Example 1 except that PBA-A obtained in Reference Example 7 was used, and Table 3 below was used.
A polyurethane having hardness and logarithmic viscosity shown in was obtained. Furthermore, using the obtained polyurethane, Example 1
A polyurethane composition was prepared in the same manner as above, and the moldability, strength, compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

Comparative Example 5 In Example 1, a PNMA containing a tin-based urethane-forming catalyst was used.
The molar ratio of -A: 1,4-butanediol: 4,4'-diphenylmethane diisocyanate is 1: 3.0: 3.9.
A continuous melt polymerization reaction was performed in the same manner except that it was 0 to obtain a polyurethane having hardness and logarithmic viscosity shown in Table 3 below. Further, using the obtained polyurethane, a polyurethane composition was prepared in the same manner as in Example 1, and the moldability, strength, compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

Comparative Example 6 In Example 1, the PMPA-A obtained in Reference Example 5 was used, and the tin-based urethane-forming catalyst-containing PMPA-A: 1, 1.
A continuous melt polymerization reaction was performed in the same manner except that the molar ratio of 4-butanediol: 4,4′-diphenylmethane diisocyanate was 1: 3.0: 4.08, and the hardness and logarithmic viscosity shown in Table 3 below were obtained. A polyurethane having was obtained.
Further, using the obtained polyurethane, a polyurethane composition was prepared in the same manner as in Example 1 to obtain moldability, strength,
The compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

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[Table 3]

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[Table 4]

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INDUSTRIAL APPLICABILITY The polyurethane composition of the present invention has remarkably improved injection moldability in spite of its low hardness, and the obtained molded product has a small compression set.
It also has excellent properties such as strength, heat resistance, and cold resistance.

Claims (1)

[Claims] 1. An [A] comprising a 3-methyl-1,5-pentanediol unit and a 1,9-nonanediol unit, and a 3-methyl-1,5-pentanediol unit and a 1,9-nonanediol unit. Molar ratio of 70:30 to 3
And diol units is 0:70, the general formula (I); dicarboxylic represented by _{-CO- (CH 2) n-CO-} (I) ( wherein, n represents an integer of 4-10) Number average molecular weight consisting of acid units of 3,000 to 7,000
Polymer diol (a), organic diisocyanate (b)
And the chain extender (c) are represented by the following formula (i); 1.02 ≦ b / (a + c) ≦ 1.08 (i) (wherein, a is the number of moles of the polymer diol, and b is the organic diisocyanate). The hardness (JIS-A) obtained by reacting at a ratio satisfying the number of moles, and c is the number of moles of the chain extender.
A polyurethane composition obtained by blending 5 to 20 parts by weight of a thermoplastic graft polymer obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyanide compound to an elastomer [B] in 100 parts by weight of polyurethane having a ratio of 80 or less.