JPH08239570A - Polyurethane resin composition - Google Patents

Abstract

(57) [Summary] [Structure] Consists of 3-methyl-1,5-pentanediol (MPD) unit and 1,9-nonanediol (ND) unit. MPD unit and ND
A diol unit in which the molar ratio of the units is 100: 0 to 30:70,
_{Formula; -CO- (CH 2) n-} CO- number average polymeric diol (a mol) of molecular weight 3,000 to 7,000 comprising a dicarboxylic acid unit (n is 4-10), organic diisocyanate (b mol) and Chain 100 parts by weight of a polyurethane having a hardness of 80 or less obtained by reacting an elongating agent (c mol) with a ratio satisfying the formula; 0.99 ≦ b / (a + c) ≦ 1.08, a higher fatty acid metal salt and / or a higher fatty acid A polyurethane resin composition comprising 0.5 to 5.0 parts by weight of bisamide. [Effect] Despite being low in hardness, the injection moldability is remarkably improved, and the obtained molded product has a small compression set and is excellent in various properties such as strength, heat resistance and cold resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane resin composition obtained by blending low hardness polyurethane with a specific lubricant. The polyurethane resin composition of the present invention is not only excellent in various properties such as strength, compression set, heat resistance and cold resistance, but also has significantly improved injection moldability, so that it can be used as a material for various molded products. It is useful.

[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. A molding material to which ordinary plastic molding methods can be applied. As
It has become widely used.

[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.

The object of the present invention is to provide a low-hardness polyurethane resin 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. Especially.

[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 the nonanediol units is 100: 0 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); 0.99 ≦ 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.
By providing 0.5 to 5.0 parts by weight of at least one of [B] higher fatty acid metal salt and higher fatty acid bisamide in 100 parts by weight of polyurethane having a ratio of 80 or less. To be done.

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 100: 0 to 30:70, and 9
It is preferably 0:10 to 30:70. When the molar ratio of the 3-methyl-1,5-pentanediol unit and the 1,9-nonanediol unit is 100: 0 to 30:70, the resulting polyurethane resin composition has good cold resistance. . 3-methyl-1,5 as a diol unit
In addition to the -pentanediol unit and the 1,9-nonanediol unit, a small amount (usually 20 mol% or less of all the diol units) of other diol units may be contained as necessary. For example, ethylene glycol, diethylene glycol, 1,4-butanediol, 2-methyl-1,3-
Examples thereof include units derived from diols such as propanediol, 1,6-hexanediol, neopentyl glycol, and 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 resin composition deteriorate. On the other hand, when the number average molecular weight of the high molecular weight diol exceeds 7,000, the productivity of the polyurethane resin composition decreases and the moldability of the resulting polyurethane resin composition becomes poor. The number average molecular weight of the polymeric 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.

The amount of the chain extender used is not particularly limited and can be appropriately selected depending on the hardness to be imparted to the polyurethane.
It is preferably used in a proportion of 0.1 to 10 mol,
It is more preferable to use it in a ratio of 3 to 7 mol.

In the production of polyurethane, the above polymer diol, organic diisocyanate and chain extender are added to the following formula (i); 0.99≤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 0.99, the resulting polyurethane resin composition has a large compression molding strain and the performance such as heat resistance deteriorates, which is not preferable. On the other hand, when the value of b / (a + c) exceeds 1.08, it becomes difficult to pelletize polyurethane during production, or sticking between pellets easily occurs. Further, since the obtained polyurethane resin composition has high adhesiveness to a metal, it is unfavorable when injection-molded because the mold releasability from the mold is poor and the appearance of the molded product is remarkably inferior.

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 a tin-based urethane-forming catalyst is used, the molecular weight of polyurethane is rapidly increased, and the molecular weight of polyurethane is maintained at a sufficiently high level even after molding, so that a polyurethane resin 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.

As the tin-based urethane-forming catalyst, for example,
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 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. The use of polyurethane having a hardness of more than 80 is not preferable because the flexibility of the obtained polyurethane resin composition is lowered. It is preferable to use polyurethane having a hardness in the range of 55 to 80 from the viewpoint that a polyurethane resin composition having a small compression set, excellent heat resistance, cold resistance and the like and improved injection moldability can be obtained. .

The logarithmic viscosity of the polyurethane used in the present invention is determined 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 since a compression set is small and a polyurethane resin composition having good mechanical performance and heat resistance can be obtained.

The polyurethane resin composition of the present invention contains 0.5 to 5.0 parts by weight of at least one lubricant selected from higher fatty acid metal salts and higher fatty acid bisamides, in 100 parts by weight of the above polyurethane. Is required
It is preferable to add 0.8 to 3.5 parts by weight. When the blending amount of these lubricants is less than 0.5 part by weight, the resulting polyurethane resin composition has a high adhesiveness with a metal, and has poor mold releasability from a mold when injection-moldable. This is not preferable because the appearance of the molded product tends to be inferior. on the other hand,
When the compounding amount of these lubricants exceeds 5.0 parts by weight, various physical properties of the obtained polyurethane resin composition are deteriorated and the surface condition of the molded product due to bleed-out tends to be poor, which is not preferable. .

The higher fatty acid metal salt has 14 to 14 carbon atoms.
Metal salts of saturated higher fatty acids of 35 are preferred. Specifically, myristic acid, pentadecylic acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cetic acid, cerotic acid, heptacosanoic acid, montanic acid, carbon number of melicinic acid, etc. Examples thereof include metal salts of 14 to 35 saturated higher fatty acids such as calcium, magnesium and zinc, and of these, calcium stearate and calcium montanate are particularly preferable.

The higher fatty acid bisamide has 1 carbon atom.
The higher fatty acid bisamide obtained by reacting a saturated higher fatty acid having 4 to 35 with an aliphatic diamine having 1 to 10 carbon atoms is preferable. Examples of saturated higher fatty acids having 14 to 35 carbon atoms in that case include myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cetic acid, serotic acid, Heptacosanoic acid, montanic acid, melissic acid, etc. can be mentioned, and examples of the aliphatic diamine having 1 to 10 carbon atoms include methylenediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine. 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane and the like. Among the higher fatty acid bisamides obtained by the reaction of the above saturated higher fatty acid and fatty acid diamine, methylenebisstearic acid amide, ethylenebisstearic acid amide, tetramethylenebisstearic acid amide, hexanemethylenebisstearic acid amide, ethylenebismontane Acid amides, tetramethylenebismontanic acid amides and hexanemethylenebismontanic acid amides are preferable, and methylenebisstearic acid amides and ethylenebisstearic acid amides are particularly preferable.

The polyurethane resin composition of the present invention can be produced by the usual polymer blending method using the above-mentioned polyurethane and lubricant. For example,
Polyurethane and lubricant are premixed 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, mixing roll, Banbury. It is manufactured by melt-kneading under heating in a batch system or a continuous system using a mixer or the like. In addition to the above lubricants, if necessary, additives such as an ultraviolet absorber, an antioxidant, a plasticizer, an antistatic agent, and a hydrolysis inhibitor may be added during mixing.

The polyurethane resin composition of the present invention can be subjected to hot melt molding and heat processing, and can be subjected to extrusion molding, injection molding,
Various molded products can be smoothly produced by any molding method such as blow molding, calender molding, and casting. Among these molding methods, it is particularly suitable as a material for injection molding.

A molded article obtained by using the polyurethane resin 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. It is useful as a material for various applications such as seats, belts, hoses, tubes, automobile parts, machine parts, shoe soles, watch bands, packing materials and damping materials.

As the molded product made of the polyurethane resin composition of the present invention, the molded product may be used as it is,
It is preferable to heat-treat (anneal) the molded product at a temperature of 60 ° C. or higher, particularly at a temperature in the range of 70 to 110 ° C., since it is possible to obtain a product having smaller compression set and more excellent heat resistance. The heat treatment time of the molded product can be appropriately selected according to the type of the polyurethane resin 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 polymer diol; hardness of polyurethane, logarithmic viscosity; strength, compression set, heat resistance, cold resistance of molded articles obtained from the polyurethane resin composition. ;
The moldability of the polyurethane resin 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 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. Thus, 12800 g of a high molecular diol (hereinafter, referred to as PNMA-A) was obtained. PNMA
The structural unit and number average molecular weight of -A are shown in Table 2 below.

Reference Example 2 5000 g of PNMA-A obtained in Reference Example 1 was added to 100
After heating to 0 ° C. and adding 150 g (3% by weight) of water thereto and heating for 2 hours with stirring to deactivate the titanium-based polycondensation catalyst, water was distilled off under reduced pressure. In this way, a polymer diol (hereinafter referred to as PNMA-B) in which the titanium-based polycondensation catalyst was deactivated was obtained. 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 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-C) in which the titanium-based polycondensation catalyst was deactivated was obtained in the same manner as in Reference Example 2. The structural unit and number average molecular weight of PNMA-C are shown in Table 2 below.

Reference Example 4 Polymeric diol 116 was prepared by carrying out 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 in which the titanium-based polycondensation catalyst was deactivated (hereinafter referred to as PMPA-A) was obtained in the same manner as in Reference Example 2. The structural unit and number average molecular weight of PMPA-A are shown in Table 2 below.

Reference Example 5 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 2. The structural unit and number average molecular weight of PNMA-D 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 in which the titanium-based polycondensation catalyst was deactivated (hereinafter referred to as PNA-A) was obtained in the same manner as in Reference Example 2. 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 2. The structural unit and number average molecular weight of PBA-A are shown in Table 2 below.

Reference Example 8 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-E) in which the titanium-based polycondensation catalyst was deactivated was obtained in the same manner as in Reference Example 2. The structural unit and number average molecular weight of PNMA-E are shown in Table 2 below.

[0049]

[Table 2]

Example 1 PNMA-B obtained in Reference Example 2 was added 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-B, 1,4-butanediol, and 4,4′-diphenylmethane diisocyanate heated and melted at 50 ° C. were mixed with tin-based urethane-forming catalyst-containing PNMA-B: 1,4-butanediol: 4,4'-
The molar ratio of diphenylmethane diisocyanate is 1: 3.
The ratio is 0: 4.08, and the total amount of these is 300.
A twin-screw extruder (30 mmφ, L / D = rotating coaxially from the 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, 0.5 parts by weight of calcium stearate and 0.5 parts by weight of ethylenebisstearic acid amide were mixed with a single screw extruder (25 mmφ, cylinder temperature: 170 to 200 ° C., die temperature: 190 ° C.). After melt-kneading, pelletize, and this pellet is 80 ℃
It was dehumidified and dried for 2 hours or more. Using the dried pellets, the moldability of the polyurethane resin composition was evaluated by the above method. Furthermore, injection molding (cylinder temperature: 170 to 200 ° C., mold temperature: 30
Disc-shaped product (diameter 120 mm, thickness 2)
(mm) was heat treated at 80 ° C. for 8 hours, and then the strength, compression set, heat resistance and cold resistance were evaluated by the above-mentioned methods. The results are shown in Table 4 below.

Example 2 The PNMA-B obtained in Reference Example 2 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-B, 1,4-butanediol, and 4,4′-diphenylmethane diisocyanate heated and melted at 50 ° C. were mixed with tin-based urethane-forming catalyst-containing PNMA-B: 1,4-butanediol: 4,4'-
The molar ratio of diphenylmethane diisocyanate is 1: 3.
A continuous melt polymerization reaction was performed in the same manner as in Example 1 except that the twin-screw extruder was continuously charged at a ratio of 0: 4.16, and had the hardness and logarithmic viscosity shown in Table 3 below. Obtained polyurethane. Furthermore, using the obtained polyurethane, a polyurethane resin 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 and Example 4 A continuous melt polymerization reaction was carried out in the same manner as in Example 1 except that PNMA-C obtained in Reference Example 3 or PMPA-A obtained in Reference Example 4 was used. A polyurethane having hardness and logarithmic viscosity shown in Table 3 below was obtained. Furthermore, using the obtained polyurethane, a polyurethane resin 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 5 A continuous melt polymerization reaction was carried out in the same manner as in Example 2 except that the PMPA-A obtained in Reference Example 4 was used to obtain a polyurethane having hardness and logarithmic viscosity shown in Table 3 below. Obtained. Further, using the obtained polyurethane, Example 2
A polyurethane resin 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 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. Further, a polyurethane resin composition was prepared in the same manner as in Example 1 except that 1.0 part by weight of calcium stearate was used as a lubricant, and moldability, strength, compression set, heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

Example 7 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, a polyurethane resin composition was prepared in the same manner as in Example 1 except that 1.0 part by weight of ethylenebisstearic acid amide was used as a lubricant, and the moldability, strength, compression set, heat resistance, and cold resistance were improved. evaluated. The results are shown in Table 4 below.

Example 8 A continuous melt polymerization reaction was carried out in the same manner as in Example 1 except that the PNMA-E obtained in Reference Example 8 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 resin 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 9 A continuous melt polymerization reaction was carried out in the same manner as in Example 1 except that PMPA-A obtained in Reference Example 1 was used without compounding a tin-based urethane-forming catalyst, and Table 3 below was used. A polyurethane having hardness and logarithmic viscosity shown in was obtained. further,
Using the obtained polyurethane, a polyurethane resin 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 1 PNMA-D obtained in Reference Example 5 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-D, 1,4-butanediol, and 4,4′-diphenylmethane diisocyanate heated and melted at 50 ° C. were mixed with tin-based urethane-forming catalyst-containing PNMA-B: 1,4-butanediol: 4,4'-
The molar ratio of diphenylmethane diisocyanate is 1: 1.
A continuous melt polymerization reaction was carried out in the same manner as in Example 1 except that the twin-screw extruder was continuously charged at a ratio of 3: 2.24, and the hardness and the logarithmic viscosity shown in Table 3 below were obtained. Obtained polyurethane. Furthermore, using the obtained polyurethane, a polyurethane resin 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 2 A continuous melt polymerization reaction was carried out in the same manner as in Comparative Example 1 except that PNA-A obtained in Reference Example 6 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 resin 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 3 A polyurethane having the hardness and the logarithmic viscosity shown in Table 3 below was obtained in the same manner as in Example 1. In the same manner as in Example 1 without adding a lubricant to the obtained polyurethane,
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 the 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 resin 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 the same manner as in Example 1, a polyurethane having the hardness and the logarithmic viscosity shown in Table 3 below was obtained. Further, a polyurethane resin composition was prepared in the same manner as in Example 1 except that 1.0 part by weight of oleic acid amide was used instead of the lubricant used in Example 1, and moldability, strength, compression set, The heat resistance and cold resistance were evaluated. The results are shown in Table 4 below.

[0063]

[Table 3]

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[Table 4]

[0065]

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

Claims (2)

[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 100: 0-3
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); 0.99 ≦ 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 resin composition obtained by mixing 0.5 to 5.0 parts by weight of at least one of [B] higher fatty acid metal salt and higher fatty acid bisamide in 100 parts by weight of polyurethane having a ratio of 80 or less. 2. The polyurethane resin composition according to claim 1, wherein the tin-based urethane-forming catalyst is blended with polyurethane in an amount of 0.5 to 15 ppm in terms of tin atom.