JPS62550A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has a improved flow characteristics while retaining excellent properties inherent to thermoplastic resins and is free from exudation and migration of a plasticizer toward the surface of the resin by thermal deterioration, containing a hydrogenated liquid diene rubber as a plasticizer. CONSTITUTION:A thermoplastic resin compsn. is obtd. by incorporating, as a plasticizer, a hydrogenated product having a hydrogenation ratio of 50-100% obtd. by hydrogenating a liquid diene rubber (liquid isoprene rubber having an average MW of 6,000-100,000 being preferred, because fluctuation in viscosity before and after hydrogenation is small), in a thermoplastic resin (e.g. polyester, polyether, polycarbonate or styrene copolymer resin). The compsn. has improved flow characteristics while retaining excellent properties inherent to thermoplastic resins and is free from exudation and migration of the plasticizer toward the surface of the resin by thermal deterioration, etc.

Description

[Detailed description of the invention] Industrial applications The present invention relates to thermoplastic resin compositions.

Conventional technology Conventionally, thermoplastic resins called engineering plastics such as polycarbonate, polybutylene terephthalate, and polyethylene terephthalate have properties such as light weight, corrosion resistance, chemical resistance, weather resistance, transparency, and electrical insulation properties. It has the following characteristics and is used depending on the requirements of various applications.

Thermoplastic resins are molded into products into desired shapes. Although the molding process varies depending on the type of thermoplastic resin, it is generally carried out at a very high temperature of 150 to 250°C. However, the fluidity of thermoplastic resins at this temperature is not necessarily sufficient. Therefore, not only does it require a lot of energy during molding, but it also causes molding defects.
This results in a decrease in product yield.

Problems to be Solved by the Invention In order to improve the fluidity of thermoplastic resins, it is possible to use plasticizers that have been commonly used in the past. deterioration of products,
Conventional plasticizers have not been fully satisfactory due to problems such as exudation and migration of plasticizers from the resulting products.

The purpose of the present invention is to make it possible! The object of the present invention is to provide a thermoplastic resin composition that has improved fluidity while retaining the excellent properties inherent to Type Ii resins. Another object of the present invention is to provide a thermoplastic resin composition in which plasticizer does not ooze or migrate to the resin surface due to thermal deterioration.

Means for Solving the Problems According to the present invention, the above object is to use a liquid diene system as a plasticizer and a hydrogenation rate of 5 to 1009 obtained by hydrogenating rubber.
This is achieved by a thermoplastic resin composition containing a hydrogenated compound of No. 6.

The liquid diene rubber used as a raw material for the hydrogenated product used in the present invention is a polymer of a conjugated diene such as getadiene, isoprene, or pentadiene, or a copolymer thereof, or a polymer of these conjugated dienes and styrene or acrylonitrile. A copolymer of a vinyl compound (a vinyl compound that can be copolymerized with a conjugated diene) that exhibits fluidity and has a low molecular weight.Specific examples include liquid polyisoprene rubber, liquid polybutadiene rubber, and liquid isogrene rubber. -butadiene copolymer rubber, liquid butadiene-fLyn copolymer rubber, liquid imprene-styrene copolymer rubber, liquid butadiene-acrylonitrile copolymer rubber, liquid isoprene-acrylonitrile copolymer rubber, and the like.

Among these, liquid isoprene rubbers such as liquid polyisoprene rubber, liquid isogrene-butadiene copolymer rubber, liquid isoprene-styrene copolymer rubber, and liquid isoprene-7crylonitrile copolymer rubber are preferred. This is because the viscosity of liquid isoprene rubber does not change significantly before and after hydrogenation, and even after hydrogenation it still shows fluidity, and the hydrogenated material improves the moldability of thermoplastic resins and
This is also because it facilitates the production of thermoplastic resin molded articles having smooth surfaces. Particularly preferred are liquid polyisoprene rubber and liquid isoprene-butadiene copolymer rubber containing 50% or more, preferably 55% or more of isoprene units. In addition, when the bonding mode of the liquid isoprene-butadiene copolymer rubber is silundum copolymer, polyisogrene block is denoted by Or B-
There are block copolymers such as I-B triblock and multiblock, and any of these is preferably used.

In the present invention, the average molecular weight of the liquid diene rubber is from s,o o to 150,0001, preferably 10,
Preferably, it is within the range of 000 to 100,000.

If the average molecular weight of the liquid diene rubber is too small,
When a hydrogenated substance from the rubber is mixed with a thermoplastic resin, the strength properties of the thermoplastic resin will be greatly reduced, and there is also a risk that the hydrogenated substance will ooze out on the surface of the resulting composition, so it is preferable. do not have. On the other hand, if the average molecular weight of the liquid diene rubber is too large, the viscosity of the hydrogenated product from the rubber will be too high and it will be difficult to handle it, and it will be difficult to mix it with the thermoplastic resin. It also causes problems. In addition, the average molecular weight means the viscosity average molecular weight (My),
The viscosity average molecular weight (Mv) is 30 in toluene solution.
Measure the intrinsic viscosity ([η]) at °C, Mv = 1.21
This can be obtained by calculating using the formula: X1o-'[η]0°77.

In the present invention, the amount of vinyl bonds in the liquid diene rubber is preferably 30% or less, preferably 20% or less. Vinyl bond amount, i.e. 1, 2 bond and/or
If the amount of 3.4 bonds exceeds 30%, the glass transition temperature of the liquid diene rubber will be high and the fluidity will be poor, which is not preferable.

Such liquid diene rubbers include natural rubber and synthetic rubber.
It can be produced by thermally decomposing a solid rubber such as 1,4-polyisoprene rubber or polybutadiene rubber, or by multipolymerizing a conjugated diene using a known method. In the present invention, since the produced liquid diene rubber contains few impurities, it is preferably produced by the latter method, that is, the polymerization method. Examples of polymerization methods include Fuji force A/polymerization, anionic polymerization, and Ziegler polymerization. Above all, it is easy to control the molecular weight, and the amount of vinyl bonds can be kept low.
In the case of isoprene-butadiene copolymer rubber, an anionic polymerization method using a lithium-based initiator is most preferred because the form of copolymerization can be easily changed.

The liquid diene rubber may have a functional group such as a carboxyl group, an acid anhydride group, or a hydroxyl group at the molecular end or in the molecular chain.

Such liquid diene rubber is made into a hydrogenated product by hydrogenation using a known method. Examples of FF reactions for hydrogenation include metals such as nickel, palladium, platinum, ruthenium or rhodium supported on carbon or alumina, heterogeneous catalysts such as Raney nickel and Urushihara nickel, or transition metal halides and aluminum, A method of using a homogeneous catalyst such as a chive two catalyst in combination with a full-kylated product of an alkaline earth metal or an alkali metal, and contacting it with hydrogen gas at a normal pressure of 200 kti/cat at room temperature to 200°C for 0.1 to 100 hours. , or p-
A method of ring formation using toluene sulfonyl hydrazide can be mentioned. Among these methods, the former catalytic hydrogenation method is preferably employed from the viewpoint of ease of reaction.

The hydrogenation reaction is carried out in a solution state by heating and melting the liquid diene rubber or by dissolving it in a reaction solvent, but from the viewpoint of reaction control it is preferably carried out in a solution state. Any reaction solvent may be used as long as it is inert to the hydrogenation reaction, but aliphatic hydrogen such as hexane and heptane or alicyclic hydrogen such as cyclohexane are most preferably used.

Depending on the reaction conditions, aromatic hydrogenated hydrogen compounds such as benzene and toluene may also be preferably used.

After the hydrogenation reaction, the catalyst is separated and removed from the reaction product by a conventional method to obtain a hydrogenated liquid diene rubber. The hydrogenated product may be used as is, but
The hydrogenated product may be further modified to contain a polar group such as a hydroxyl group, a carboxyl group, or a halogel group at the molecular end or side chain.

In the present invention, the hydrogenation rate of liquid diene rubber means the proportion of carbon-carbon unsaturated double bonds in the liquid diene thread rubber that are hydrogenated, and in the present invention, the hydrogenation rate is 50%.
-100%, preferably 70-100%. If the hydrogenation rate is too low, the heat resistance of the hydrogenate itself will decrease, and the hydrogenate will suffer from thermal deterioration when mixed with a thermoplastic resin at high temperatures or when the resulting composition is molded and used. Otherwise, various physical properties of the thermoplastic resin, including its strength, will deteriorate. The hydrogenation rate is determined by determining the iodine value before hydrogenation and the iodine value after hydrogenation, and calculating the percentage of the latter relative to the former.

The hydrogenated liquid diene rubber thus obtained is used as a plasticizer for thermoplastic resins.

Thermoplastic resins preferably used in the present invention include thermoplastic resins having an ester bond, ether bond, thioether bond, or amide bond in the main chain, and resins obtained by copolymerizing styrene as one component. Examples of the former include saturated polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyarylates (fully aromatic polyesters), polycarbonates (carbonate type polyester/l/L polyacetal, polyphenylene oxide, polyether ether ketone,
Examples include polyetherimide, polysulfone, polyethersulfone, polyphenylene sulfide, and polyamide. Examples of the latter include AESVfJ resin (acrylonitrile-butadiene-styrene resin), AS resin (acrylonitrile-styrene resin), AAS resin,
There are ES resin, AC8 resin, etc.

The hydrogenated liquid diene rubber thus obtained is used as a plasticizer for thermoplastic resins.

Thermoplastic resins preferably used in the present invention include thermoplastic resins having an ester bond, ether bond, thioether bond, or amide bond in the main chain, and styrenic copolymer resins obtained by copolymerizing styrene as one component. It will be done. Examples of the former include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycarbonate (carbonate type polyester/I/), polyethers such as polyacetal, polyphenylene oxide, polyether ether ketone, polyether imide, etc. Examples include polythioethers such as sulfone, polyether sulfone, and polyphenylene sulfide, and polyamides. Examples of the latter include ABS resin (acrylonitrile-butadiene-styrene resin), ASIM resin (acrylonitrile-styrene resin), AAS resin, ABS resin, AC8 resin, and the like. These resins may be used alone or in combination of two or more.

The amount of the hydrogenated liquid diene rubber used in the thermoplastic resin composition of the present invention may be small as in the case of conventional plasticizers, but it may be in an amount that greatly exceeds the amount used as a plasticizer. Specifically, it is within the range of 0.5 to 70% by weight, preferably 1 to 50% by weight, and even more preferably 1 to 15% by weight based on the total amount of the thermoplastic resin and hydrogenated material.

The thermoplastic resin and the hydrogenated liquid diene rubber can be mixed using an internal mixer such as a Banbury mixer, a kneader, or a Henschel mixer, a #-y'' ring, or a twin-screw extruder. The resulting mixture can be processed by press molding, injection molding, transfer molding,
It is formed into a film, sheet, tube, rod, or various shapes by calendering or the like.

In addition, when mixing, if necessary, stabilizers such as anti-aging agents and ultraviolet absorbers, lubricants, pigments, fillers, or reinforcing fibers may be used.

The thermoplastic resin composition of the present invention has improved fluidity and exhibits excellent moldability. Therefore, it is possible to reduce the energy cost required during molding.

Furthermore, it is possible to shorten the molding time and improve productivity. Furthermore, due to its excellent fluidity, even when using molds with complex shapes, it is possible to fill even the smallest details, making it easy to manufacture molded products with minute shapes and with a high yield rate. can be done.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A liquid polyisoprene rubber (abbreviated as LIR in Table 1) having an average molecular weight of 125,000 and a vinyl bond content of 12% was obtained by polymerizing isoprene using n-butyllithium as a catalyst. This liquid polyisoprene rubber was dissolved in cyclohexane in an autoclave to form a 20% by weight solution. To this solution, 2J1% by weight of Baodium (5% by weight) - carbon-supported catalyst was added and dispersed, and oxidized by hydrogen.
A hydrogenation reaction was carried out at 50° C. under pressure of 0 to 9/C-11.

After the reaction was completed, the catalyst was separated by filtration and vacuum dried to obtain a hydrogenated liquid polyisoprene rubber.

The hydrogenation rate determined by measuring the iodine value was 99%.
Met. Hydrogenated liquid polyisoprene having a hydrogenation rate of 93.85 was prepared in the same manner as above except that the reaction time of the hydrogenation reaction was changed.

Using each of the obtained hydrogenated products and polycarbonate, the first
A polycarbonate mixture was obtained by kneading at 280° C. for 5 minutes according to Prabender Plastograph at the blending ratio shown in the table. In addition, as a measure of the fluidity of this mixture, the torque of the rotating shaft immediately before the end of crosstalk was measured. The obtained mixture was press-molded to prepare a test piece for a tensile test, and the tensile strength and elongation were measured using an Instron universal tensile tester. The results are shown in Table 1.

Below is the blank space 1 Table υ Idemitsu Petrochemical ■ A-3000 2 Torque of the rotating shaft just before the end of kneading From the above table, by mixing the water MFA additive of liquid polyisogrene rubber with polycarbonate, the torque of the rotating shaft just before the end of kneading of the mixture It can be seen that the torque of the rotating shaft is significantly reduced, and the fluidity of the mixture is improved. Moreover, despite the decrease in fluidity, the tensile strength of the test pieces from the obtained mixture hardly decreased, indicating that the addition of the hydrogen additive had little effect on the physical properties.

Example 2 Polyethylene terephthalate was prepared in the same manner as in Example 1 using the hydrogenated liquid polyisogrene rubber obtained in the same manner as in Example I and polyethylene terephthalate in the blending ratios shown in Table 2. A mixture was prepared.

A test piece was prepared from the mixture, and the yield stress was determined from the test piece. The results are shown in Table 2 along with the torque of the rotating shaft just before the end of kneading.

As is clear from Table 2, although the addition of hydrogenated liquid polyisoprene rubber improves the fluidity of polyethylene terephthalate, it has little effect on the yield pressure.

Example 3 Liquid polyisoprene rubber with an average molecular weight of 49,000 was obtained by combining isoprene with n-butyllithium. The liquid polyisoprene rubber was dissolved in hexane in an autoclave, and 20M 1k% was obtained. A solution of

To this, a catalyst solution prepared by mixing cobalt triethylaluminum naphthenate in hexane at a molar ratio of 1:5 was added in an amount such that cobalt was 0.1 mol% based on the isoprene units in the liquid polyisoprene rubber, and hydrogen The pressure was increased and the hydrogenation reaction was carried out at 50°C. After the reaction was completed, the product solution was poured into a large amount of methanol containing a small amount of hydrochloric acid to precipitate the product, and the product was dried under vacuum to obtain a hydrogenated liquid polyisogrene rubber. The hydrogenation rate was 99%. Further, a hydrogenated product with a hydrogenation rate of 85% was obtained by the same method as above except that the reaction time of the hydrogenation reaction was changed.

The thus obtained hydrogenated product, polycarbonate, and acrylonitrile-butadiene ethylene resin were used in the proportions shown in Table 3, and kneaded for 5 minutes at 280° C. using a Prabender Plastograph to prepare a mixture. The torque of the rotating shaft just before the end of kneading was measured and used as a measure of fluidity.

In addition, the strength properties were investigated using the same method as in Example 1. The results are shown in Table 3. In addition, the mixture was heated to 80℃
[After being left in a hot water bath for 20 days, the surface was observed, and no oozing of the hydrogenated product of liquid polyisoprene was observed.

Table 3 (Table 3) 2 Rohm and Haas KM-3303 Torque of the rotating shaft just before the end of kneading Effects of the invention The thermoplastic resin composition of the present invention has improved properties while retaining the excellent properties inherent to thermoplastic resins. It has good fluidity. Moreover, the plasticizer does not ooze or migrate to the resin surface due to thermal deterioration or the like.

Claims (6)

[Claims] (1) A thermoplastic resin composition containing a hydrogenated material with a hydrogenation rate of 50 to 100% obtained by hydrogenating a liquid diene rubber as a plasticizer. (2) The composition according to claim 1, wherein the liquid diene rubber is a liquid polyisoprene rubber. (3) The composition according to claim 1, wherein the liquid diene rubber is a liquid isoprene-butadiene copolymer rubber. (4) The average molecular weight of the liquid diene rubber is 6,000 to 1
A composition according to any one of claims 1, 2 or 3, wherein the composition is 00,000. (5) The composition according to claim 1, wherein the thermoplastic resin is polyester, polycarbonate, polyether, polythioether, or polyamide. (6) The composition according to claim 1, wherein the thermoplastic resin is a styrene copolymer resin.