JPS5891762A - Thermoplastic polyurethane resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. consisting of a specified benzoate ester compd. and a thermoplastic polyurethane resin and exhibiting excellent compability and moldability. CONSTITUTION:A benzoate ester compd. (A) of the formula (where R is arylene, alkylene, cycloalkylene or CnG2n-CnH2n; compd. (e.g. ethylene glycol) at 150- 250 deg.C for 15-25hr in nitrogen gas. Then 1-50wt% (A) is premixed with (B) 99- 50wt% thermoplastic polyurethane resin, followed by melt blending at 150- 220 deg.C. EFFECT:The compsn. retains excellent moldability even when kept under the optimum conditions of heat forming for long hours and produces molding products with high strength and elongation retention rate. USE:Tube, roll, artificial leather, cable sheathing, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic polyurethane resin composition that has significantly improved moldability during thermoforming processes such as injection molding, extrusion molding, and calendar molding.

Recently, thermoplastic polyurethane resins have been applied to various yuzu applications using thermoforming processing machines such as injection molding, extrusion molding, and calendar molding, but during these processing, the residence time at the optimum molding temperature is If the length is too long, the thermal stability will be compromised, various molding defects will occur frequently, tackiness will occur, the releasability from the mold will be poor, and there will be many problems in molding processability. It is known that the physical properties of the obtained molded product, particularly its strength, are significantly different depending on the length of the S drop time.

The present inventors have discovered various cooling agents such as heat-resistant stabilizers and lubricants, as well as 1-heat 1=TV polyurethane and B
We have specifically investigated ways to improve the molding processability of polyurethane resins, focusing on compositions with Sm, fats, or AS fallen fats. In addition, the physical properties of the resulting molded product are significantly deteriorated, and there are many problems such as bleeding and pluming due to poor compatibility. Ta.

Therefore, the present inventors conducted further research and found that extremely limited benzoic acid yarn ester components and heat 6 fm
The resin composition with polyurethane copper resin has extremely good properties, and also maintains excellent moldability even when kept in oil for a long time under the optimum molding conditions during thermoforming. In terms of physical properties, the resulting molded product exhibits excellent strength and elongation retention, which led to the completion of the present invention.

That is, the present invention provides a thermoplastic polyurethane side fat composition comprising 1 to 501% by weight of the compound represented by the general formula [■] and 1150 to 99% by weight of a thermoplastic polyurethane side fat. It is a begging offer.

The compound represented by the general formula [I] used in the present invention is represented by R in the formula, arylene group, alkylene group, 4'J, cycloalkylene group, or CnH2n-()-CnH2
represented by n (however, n is 1 to 150, preferably 1
It is a benzoic acid thread diester (having an integer of 100 to 100), which is produced from a benzoic acid thread and a dihydroxy compound under a nitrogen stream at 150 to 250°C, 15 to 25°C.
It is synthesized under the condition of time.

The dihydroxy compounds mentioned here include ethylene glycol, clopylene glycol, linear glycols such as 1,4-phthanediol, diethylene glycol, alkyl ether glycols such as diethylene glycol, bisphenol A, and bisphenol A. Any compound having two hydroxyl groups such as aromatic glycols such as alkylene oxide adducts may be used. Examples of the compound represented by the general formula CI) include diethyl ether dibenzoic ester, dipropyl ether dibenzoic ester, ethyl dibenzoic ester, and tetramethylene dipene zoic ester.

The amount of this compound to be used is 1 to 50% by weight (hereinafter referred to as %) in the thermoplastic polyurethane, preferably 5 to 60%, but less than 1% (or 50%).
Even more than this is not preferable because it causes problems in moldability, kashiwamochi properties, strength, etc.

3% thermal af plastic polyurethane used in the present invention [1
1] may be any commonly used compound, for example, a dioxy compound having an average molecular weight of 500 to 5,000.
al and (05 to 10 moles of carbon atoms per mole of al)
A polyol obtained from 1al, (b) +lIK equal number of moles of organic diisocyanate-Hcl of
Plastic polyurethane or the like is preferred.

Here, the dioxy compound having a molecular weight of 500 to 5,000 is, for example, poly(tetramethylcarbonyloxy)glycol prepared from butanediol and adipic acid, or poly(tetramethylcarbonyloxy)glycol prepared from ethylene glycol and adipic acid. Dihydroxypolyesters derived from aliphatic dihydro-I' compounds such as poly(ethylV-tetramethylenetriponyloxy)glycol and alkylene dicarboxylic acids, or poly(IA-shielded from ε-caprolactone).
Examples thereof include polylactone glycols prepared by ring-opening polymerization of alkyl-substituted lactones such as pentamethylene carbonyloxy) glycol, and polytetramethylene ether glycols produced from tetrahydro-6=-furan.

In addition, unsubstituted glycols having 2 to B carbon atoms include ethylene glycol, propylene glycol, 1゜4-butanediol, diethylene glycol, 1,6-hexamethylene dalicol, etc. .

Examples of organic isocyanates include aromatic isocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI, and xylene diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.

The method for producing the composition of the present invention is to maintain the benzoic acid thread diester [I] in a homogeneous mixed state in the dioxy compound a) during the production of the thermoplastic polyurethane steel (II). Unsubstituted glyco-/L(b)
, organic diisocyanate) (c+ at a predetermined ratio)
Plastic polyurethane (can be easily synthesized according to the conventional fat end method.

Another method is to mix pelleted, powdered, or pulverized plastic polyurethane sanitary resin CIO for pA with liquid or powdered diester [I]Y+5r in a constant ratio in a normal vertical or horizontal mixer. It is produced by premixing using a mixing roll, mixing extruder, internal mixer, etc., and then carrying out bath-melt fermentation at 150 to 220°C.

The thermoplastic polyurethane resin composition of the present invention, like conventional thermoplastic polyurethane resins, is composed of cyclized vinyl resin, ABst + resin, AS + resin, polyester elastomer resin, PBT resin, etc. The polyurethane resin composition of the present invention can be used not only alone, but also in polymer blends with other oak resin compositions, using general-purpose thermoforming machines such as injection molding, extrusion molding, and calender molding. In addition, the thermal m1M1i polyurethane composition of the present invention can be molded into various uses using various thermoforming machines, such as tubes, rolls, backings, belts, films, synthetic leather, shoe soles, and skis. It can be used for parts such as electric wire coating and automobile parts paulownia.

Next, the present invention will be specifically explained with reference to Examples. In the examples, the molding temperature is the highest among various thermoforming machines.
A study on injection molding processing, where the difference in length and shortness of one-time boiling time is especially noticeable in terms of molding processability and physical properties, will be described in living organisms.

Note that "1 part" means "1 part by weight".

Synthesis Example 1 (Synthesis of Diester) Ethylene glycol 620'JS (10 moles) and benzoic acid 2,440 m (20 moles) were weighed into a 5E four-loaf flask equipped with a stirrer, thermometer, and 9-condenser. , Stir and heat at 150 to 220°C in a nitrogen stream for 15 to 20 hours, dehydration degree Lt, '1, acid 1 time 0.5. 2.700 parts of diester raw material having 4 OH and 10 parts were obtained.

Synthesis example 2 (synthesis of diester) Diethylene glycol 1,0
60 cities (10 moles) and benzoic acid 2.440
f411 (20 mol) also has an acid value of 0. Ro, OH value 1.0
5.140 parts of diester product were obtained.

Synthesis Example 6 (Production of thermoplastic polyurethane resin) Poly(pentamethylene carbonyloxy) with a molecular weight of approximately 2,000
After vacuum drying 3,000 parts (1.5 mol) of glycol in a kneader at 80°C for 20 minutes, 165 parts (15 mol) of tetramethylene glycol was added, thoroughly mixed at 90°C, and diphenylmethane was added at the same temperature. -4,4'-Diisocyanate 10-750 (6.0 mol) was added and stirred for 10 minutes.

The lumpy reaction product was taken out and heated at 160°C for 1 hour.
The mixture was cooled and crushed with a hammer to produce a pulverized thermoplastic polyurethane resin.

Synthesis example 4 (manufacture of thermoplastic polyurethane resin) Synthesis example 3
Polybutylene ether glycol 3,0008 (5.0 mol), tetramethylene glycol 135s (1.5 mol) and diphenylmethane-4,4'-diisocyanate 1.125 mol.
A translucent thermoplastic polyurethane resin was produced from Miyako (4.5 mol).

Example 1 Molecular weight approx. 2. After drying 3,000 keq (1.5 mol) of ODD poly(pentamethylene carbonyloxy) glycol in a kneader at 80°C for 20 minutes, 685.5 ft11 (15 mol) of the diester synthesized in Synthesis Example 1 was added. 'm
Elm%) and tetramethylene glycol 135 MIS (1,
Add 750 m (3,0 m) of diphenylmethane-4,4'-diynthate at the same temperature and mix thoroughly at 90°C
mol) and stirred and mixed for 10 minutes. The lumpy reaction product was taken out, aged at 160°C for 1 hour, cooled and crushed with a hammer, and the crushed product was put into an extruder and extruded at 160-180°C to form a transparent pellet-shaped hot mouth polyurethane. A specific JAiIr composition was prepared.

During the injection molding process of this resin composition under optimal processing conditions, the moldability and physical properties should be evaluated by changing the oil reservoir time in the cylinder (6. 10U in length 150mm with injection molding processing at each residence time of 1 minute, 7 minutes, and 15 minutes.
A test heath of imX Kusa 2 City was prepared and subjected to the following injection molding processability and each qvJ property test. In addition, as a comparison column, the thermal iJ' plastic polyurethane obtained in Synthesis Example 6
1 was used.

[Injection molding processability]

6.5oz in-line screw set injection molded,
The most severe terrain conditions that can be molded in the normal cycle (90 seconds), after leaving the cylinder for 1 to 15 minutes, injection pressure cuff 0 D KW/cyn'', injection time 20 seconds,
A test piece molded product having a length of 150 mm, 1100 mm, and a thickness of 2 mm was injection molded under constant cooling conditions of a cooling time of 40 seconds and a mold temperature of 20°C. Visual observations were made to check for the occurrence of defective phenomena such as ``bubble'' and the presence or absence of stickiness in the mold when the molded product was released.

[Tensile strength retention rate]

The test piece obtained by the above injection molding process is JISK
The tensile strength was measured according to the -6301 method. Next, the tensile strength of the test piece was adjusted to 100% for 1 minute in the cylinder.
Then, the tensile strength retention rate at each residence time was determined.

15- [Elongation retention rate] 1 Rime tensile strength 1 meter retention rate Same as JISK-63 (
] According to method 1, the tensile strength retention rate was determined by 0. [Tear strength retention rate] Similarly to the above tensile strength retention rate, both legs were rubbed according to the JISK-6501 method, and the tear strength retention rate was determined by 1.

[Phase F6 cases] Injection molding) Test pieces obtained in J11 process were heated to temperature 7.
The test pieces were left in a constant temperature and humidity chamber at 0° C. and 98% humidity for 20 days, and the presence or absence of defective phenomena such as “bleed” and “prime” on the surface of the test pieces was observed.

The above results are shown in Table 1 below.

Example 2 Diester resin 0-55 synthesized in synthesis row 2 and thermoplastic polyurethane resin 100-45 synthesized in synthesis example 4
After preliminary mixing using a high-speed mixer, the mixture was melt-kneaded using a screw extruder at a molding temperature of 170 to 190°C to produce a homogeneous thermoplastic polyurethane composition.

These resin compositions vIJ were subjected to injection molding workability and physical property tests at Machi-sama in Example 1d. Further, as a comparative example, a case where the @ song of the present invention was skipped was given.

The following Table 2 shows the results of various tests after the cylinder was left for 15 minutes during the injection molding process.

Claims (1)

[Scope of Claims] A thermoplastic polyurethane resin composition comprising 1 to 50 J&% of a compound represented by general formula CI) and 50 to 991% of a thermoplastic polyurethane resin (fI).