JPH07331044A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Structure] A thermoplastic resin composition obtained by combining a polycarbonate resin, a polyester polymer, and a block copolymer having a hydroxyl group at the terminal. [Effect] When the thermoplastic resin composition of the present invention is used, the solvent resistance and chemical resistance of the polycarbonate resin can be improved without lowering the impact resistance of the polycarbonate resin.

Description

Detailed Description of the Invention

[0001]

[Industrial applications]

The present invention relates to a thermoplastic resin composition composed of a polycarbonate-based polymer and a polyester-based polymer, and in particular, it comprises a polycarbonate-based resin and a polyester-based polymer and a specific block copolymer having a hydroxyl group added to the terminal. It relates to a thermoplastic resin composition comprising a mixture.

[0003]

2. Description of the Related Art Polycarbonate polymers have excellent properties such as transparency, impact resistance, heat resistance and dimensional stability, and are used in a wide variety of fields such as electricity, electronics and automobiles. However, this polycarbonate-based resin has a problem in durability against chemicals and solvents, and has a big defect that cracks are generated when it comes into contact with these substances, and further has a defect that fluidity is insufficient. .

Further, polyester polymers have been used in various fields such as electric parts, electronic parts, automobile parts, and industrial machine parts in recent years by taking advantage of their excellent heat resistance, solvent resistance, molding processability and the like. Widely used.

A method of blending this polyester resin has been adopted for the purpose of improving the drawbacks of the above polycarbonate resin. Although the chemical resistance is improved by blending both of them, there are drawbacks such as a decrease in fluidity and a decrease in impact resistance. In particular, impact resistance is a major feature of polycarbonate resins, and impairing this is a serious drawback.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to obtain a thermoplastic resin composition comprising a polycarbonate polymer and a polyester polymer without impairing impact resistance.

[0007]

According to the present invention, the above-mentioned object can be achieved by a composition obtained by mixing a mixture of a polyester polymer and a block copolymer having a hydroxyl group at the terminal with a polycarbonate resin.

More specifically, a polycarbonate resin,
Polyester polymer, and polymer block mainly composed of aromatic vinyl compound and 1,2-bond content of 20%
At least one block A selected from the group consisting of hydrogenated polybutadiene blocks obtained by hydrogenating the following polybutadiene, hydrogenated polyisoprene blocks, and polybutadiene having a 1,2-bond content of 30 to 70% A hydrogenated polybutadiene block obtained by hydrogenation and a block copolymer containing at least one block selected from the group consisting of hydrogenated isoprene and a random copolymer block of butadiene have a hydroxyl group at the end. Modified block copolymer having at least one polymer block mainly composed of a modified block copolymer and / or an aromatic vinyl compound and at least one polyisobutylene block having a hydroxyl group at the terminal It is achieved by a composition containing Hereinafter, the present invention will be described in detail.

The polycarbonate resin used as the component (a) in the resin composition of the present invention is a polymer having a carbonic acid ester structure in the main chain, and is bisphenol A.
The carbonic acid ester structure of is used.

The polyester polymer used as the component (b) is a dicarboxylic acid such as an aromatic dicarboxylic acid, p-hydroxy aromatic carboxylic acid or an aliphatic dicarboxylic acid, and a diol such as an aromatic diol or an aliphatic diol. Polymers obtained by polycondensation of a suitable combination or ring-opening polymerization of lactones such as caprolactone and valerolactone, and polyethylene terephthalate, polybutylene terephthalate, polyarylate, poly p-hydroxybenzoic acid. Typical examples thereof include polymers, polyethylene naphthalate, polybutylene naphthalate, poly 1,4-cyclohexane dimethylene terephthalate, and polycaprolactone.

As the dicarboxylic acid used here,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenecarboxylic acid,
Aromatic dicarboxylic acids such as 4,4-diphenylcarboxylic acid, 4,4-diphenylethercarboxylic acid and 1,2-bis (phenoxy) ethane-4,4-dicarboxylic acid, and fats such as succinic acid, adipic acid and sebacic acid Group dicarboxylic acids, their ester-forming derivatives and the like can be mentioned. These dicarboxylic acids may be used alone or in combination of two or more.

As the other component diol, ethylene glycol, 1,4-butanediol,
Propylene glycol, neopentyl glycol, 1,
Aliphatic diol having 2 to 10 carbon atoms such as 5-pentanediol, 1,6-hexanediol, decamethylenediol, cyclohexanediol; molecular weight of 6000 or less such as polydiethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol The polyalkylene glycol and the like can be mentioned. These copolymerized diol components may be used alone or in combination of two or more.

Further, the polyester-based polymer contains a small amount of a trifunctional or higher-functional copolymerization component such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid, as long as its properties are not significantly affected. You can leave.

Of the above various combinations, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are more preferably used.

The polyester polymer used in the present invention can be manufactured by a conventionally known method, and its manufacturing method is not particularly limited. Further, the intrinsic viscosity and the like of the polyester-based polymer may be any in the usual range.

Further, the block copolymer having a hydroxyl group at the terminal of the component (c) used in the resin composition of the present invention can be obtained by an anionic polymerization method or a cationic polymerization method.

The block copolymer having a hydroxyl group at the terminal obtained by the anionic polymerization method is an aromatic compound such as styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene and 2-vinylnaphthalene. A block obtained by polymerizing vinyl, or one or more blocks (block A) selected from polybutadiene blocks obtained by polymerizing a butadiene monomer such that 1,4 bonds are 60% or more; 1,2 bond or 3, with isoprene block or isoprene monomer
Polyvinyl isoprene block polymerized to have 4 bonds of 30% to 60%, or a random copolymer block of isoprene and butadiene, or butadiene monomer having 1,2 bonds of 30% to 60% A hydroxyl group is added to the end of a block copolymer having at least one block (block B) selected from the polymerized polyvinyl butadiene blocks, and the double bond in the block composed of a conjugated diene is hydrogenated. It was done.

In the block copolymer having a hydroxyl group at the terminal, the block A and the block B are (AB) p-OH (BA) q-OH A- (BA) r-OH. And B- (AB) s-OH (in the formula, p, q, r, and s each represent an integer of 1 or more, and OH represents a hydroxyl group). Although p, q, r and s can be arbitrarily determined, they are usually selected from the range of 5 or less. The block copolymer having a hydroxyl group at the terminal may be used in a state where two or more kinds of block copolymers having a hydroxyl group at the terminal are mixed depending on the case.

The block copolymer having a hydroxyl group at the terminal can be obtained by obtaining a polymer by anionic living polymerization or the like using a commonly used organic alkali metal catalyst, adding the hydroxyl group to the terminal, and then hydrogenating the polymer. . For example, (AB) p-OH or A- (BA) r
To polymerize —OH, hexane, using an anionic polymerization initiator such as n-butyllithium or s-butyllithium,
Using a saturated aliphatic hydrocarbon compound such as heptane or cyclohexane, or an aromatic hydrocarbon compound such as benzene or toluene as a solvent, the aromatic vinyl monomer or the butadiene monomer is added under the temperature condition of 30 to 60 ° C. A living polymer is produced by anionic polymerization, and then an isoprene monomer is dropped into the system to obtain a binary block copolymer. Furthermore, if an aromatic vinyl monomer or a butadiene monomer is dropped again into the system, a ternary block copolymer can be produced. By repeating this operation, a block copolymer of 4 or more elements is obtained. On the other hand, in order to polymerize (BA) q-OH or B- (AB) s-OH, an isoprene monomer is anionically polymerized to produce a living polymer, and then an aromatic vinyl monomer is used. Alternatively, butadiene is dropped into the system to obtain a binary block copolymer. Furthermore, a ternary block copolymer can be produced by dropping the conjugated diene-based monomer again into the system. By repeating this operation, a block copolymer of 4 or more elements is obtained. The polyvinyl butadiene block can be obtained by adding dioxane or tetrahydrofuran to the system in an appropriate amount and dropping a butadiene monomer. Similarly, the polyvinyl isoprene block can be obtained by adding an appropriate amount of dioxane or tetrahydrofuran to the system and dropping the isoprene monomer. Then, when the block copolymer reaches a desired molecular structure and molecular weight, ethylene oxide or propylene oxide is added, and then alcohols, carboxylic acids, water, etc. are added to terminate the polymerization.

Subsequently, the obtained copolymer is hydrogenated to produce a block copolymer having a hydroxyl group at the terminal. A homogeneous catalyst or a heterogeneous catalyst can be used as the hydrogenation catalyst. When using a homogeneous catalyst, an organic transition metal catalyst (for example, nickel acetylacetonate,
Cobalt acetylacetonate, nickel naphthenate,
0.01 to 0.1 mol% per double bond of the polymer subjected to hydrogenation of a Ziegler catalyst or the like, which is a combination of an alkyl compound of a metal such as cobalt naphthenate) and aluminum, an alkali metal or an alkaline earth metal Use to some extent. Hydrogenation reaction is from room temperature to 150 ° C, normal pressure to 50 kg / cm
It is performed under a hydrogen pressure of ² and is completed in about 1 to 50 hours. After completion of the reaction, acidic water is added to the vessel and vigorously stirred to dissolve the hydrogenation catalyst in water. By removing the aqueous phase from the two phases that have been phase-separated and further distilling off the solvent, a block copolymer having a hydroxyl group at a desired end is obtained.

In the block copolymer having a hydroxyl group at the terminal used in the present invention, it is necessary that 50% or more of the carbon-carbon double bond in the block composed of the conjugated diene monomer is hydrogenated. From the viewpoint of deterioration and weather resistance, the hydrogenation rate is preferably 80% or more.

The block copolymer having a hydroxyl group at the terminal obtained by the cationic polymerization method is an aromatic vinyl compound such as styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene or p-chlorostyrene. Copolymerization of a block obtained by polymerizing one or more kinds or a block obtained by polymerizing indene and its derivative (block A) and a polyisobutylene block obtained by polymerizing isobutylene (block B) A hydroxyl group is added to the end of the united product.

The block copolymer having a hydroxyl group at the end is obtained by a conventional cationic living polymerization using 1,4-di (2-methoxy-2-propyl) benzene or the like to add a hydroxyl group to the end. Obtained by For example, in order to obtain a styrene-isobutylene-styrene triblock copolymer, 1,4-di (2-methoxy-) is used in a solvent of cycloalkane such as cyclohexane and methylcyclohexane, or halogenated alkane such as methyl chloride and methylene chloride. A living polymer is produced by cationically polymerizing a monomer of isobutylene under the temperature condition of -10 ° C to -90 ° C using 2-propyl) benzene and titanium tetrachloride as an initiator, and then N, N-dimethylacetamide and After adding 2,6-di-t-butylpyridine, a styrene monomer is dropped into the system to obtain a styrene-isobutylene-styrene triblock copolymer having chlorine at both ends. By repeating this operation, a block copolymer of 5 or more units is obtained. Then, dehydrochlorination, hydroboration, and oxidation are performed to obtain a styrene-isobutylene-styrene triblock copolymer having hydroxyl groups at both ends.

The hydroxyl group of the block copolymer having a hydroxyl group at the terminal may be added to either the block A terminal or the block B terminal, but the one added to the terminal of the block A, which is a hard block, is preferably styrene. The one added to the end of the block is most preferably used. The number average molecular weight of the block A of the block copolymer having a hydroxyl group at the terminal is preferably in the range of 5,000 to 50,000. The number average molecular weight of block B is 10,000
It is preferably in the range of -100,000. Further, the number average molecular weight of the entire block copolymer is 15,000 to 1500.
Those in the range of 00 are used. The weight ratio of block A to block B is not particularly limited, but is 1: 9 to 7:
Those in the range of 3 are preferably used.

The concentration of terminal OH groups must be 0.5 or more per molecule. When the concentration of OH groups is less than the above range, it becomes difficult to maintain high mechanical properties of the composition of the present invention. From this viewpoint, the concentration of OH groups is more preferably 0.7 or more.

In the polymer composition of the present invention, the ratio of the polyester polymer and the block copolymer having a hydroxyl group at the terminal is such that the weight ratio of the polyester polymer and the block copolymer having a hydroxyl group at the terminal is 98 / 2 to 45 /
It is preferably in the range of 55. When the proportion of the block copolymer having a hydroxyl group at the terminal is more than 45% by weight, the heat resistance, solvent resistance, mechanical properties and the like of the finally obtained resin composition cannot be exhibited. Further, in the finally obtained resin composition in which the proportion of the block copolymer having a hydroxyl group at the terminal is less than 2% by weight, the effect of improving impact resistance becomes small, which is not preferable. From this viewpoint, the proportion of the polyester polymer in the resin composition is more preferably 95 to 60% by weight.

Further, in the resin composition of the present invention, the ratio of the polycarbonate resin to the mixture of the above polyester polymer and the block copolymer having a hydroxyl group at the terminal is such that the polycarbonate resin, the polyester polymer and the terminal are mixed. It is preferable that the weight ratio with respect to the total of the block copolymer component having a hydroxyl group is 95/5 to 30/70. When the ratio of the mixture of the polyester polymer and the block copolymer having a hydroxyl group at the terminal is smaller than the above range, the effect of improving the chemical resistance cannot be obtained, and when the ratio exceeds the above range, the mixture can be obtained by mixing. Decrease in elastic modulus of the composition,
The decrease in impact resistance is too large, which is not preferable. From this viewpoint, the ratio is more preferably 90/10 to 60/40.

The resin composition of the present invention can be produced by mixing the above-mentioned three kinds of components and, if necessary, other additives simultaneously or sequentially and melt-kneading by a conventional method. Melt-kneading can be performed using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader or a Banbury mixer. The type of equipment used and the melt-kneading conditions are not particularly limited, but kneading is generally performed at 180 to 270 ° C. for 3 to 30 minutes.

In some cases, by coexisting the block copolymer when polymerizing the polyester resin, it is possible to obtain a mixture of the polyester resin and the block copolymer at the end of the polymerization of the polyester.

The composition of the present invention optionally contains styrene-isoprene, styrene-, which does not have a terminal functional group.
Hydrogenated product of butadiene block copolymer, polystyrene,
Styrene-based resins such as ABS and other various thermoplastic resins, reinforcing agents such as glass fibers, fillers such as mica and talc, antioxidants, release agents, colorants, ultraviolet absorbers, antistatic agents, crystal nucleating agents, It may contain various additives such as flame retardants.

The composition of the present invention has features such as excellent chemical resistance and solvent resistance, generation of cracks due to adhesives, and prevention of deterioration of durability due to solvent, gasoline, grease and the like.

The polymer composition of the present invention can be molded by any molding method such as injection molding, extrusion molding, press molding, blow molding, extrusion blow molding, calender molding, cast molding and the like. It is possible to manufacture a molded product of any shape and application such as parts, electronic parts, machine parts, automobile parts, pipes, sheets, films, daily necessities and the like. Since it has a high degree of impact resistance and chemical resistance, it is particularly suitably used for automobile parts which are coated and used.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following Examples and Comparative Examples, each polymer is shown by an abbreviation, and the specific contents are shown in Table 1 below.

[0034]

[Table 1]

(Production of Block Copolymer Having Hydroxyl Group at Terminal) Production Examples 1 and 2 Styrene, isoprene, and styrene are sequentially polymerized in cyclohexane with s-butyllithium as an initiator, and after polymerization is completed, the polymerization active terminal is introduced. Then, a 10-fold molar amount of ethylene oxide was added to obtain a copolymer having an S-I-S structure having a hydroxyl group at one end of the molecular chain. Further, by hydrogenating this, SEPS having a terminal hydroxyl group
-OH (I) was obtained. Further, SEPS-OH (II) was obtained by changing the amount of the monomer used. The molecular properties are shown in Table 2.

Production Example 3 S was similarly prepared by using butadiene instead of isoprene.
EBS-OH (III) was obtained.

Production Example 4 After the polymerization was completed, the same procedure as in Example 1 was carried out without adding ethylene oxide, and a block copolymer having no terminal functional group, SE
PS (IV) was obtained.

[0038]

[Table 2]

(Examples 1 to 5 and Comparative Examples 1 to 4) The polymers shown in Tables 1 and 2 were blended at 250 ° C. in a twin-screw extruder at the weight ratios shown in Table 3 below. A test piece was prepared by injection molding at 270 ° C. using the compound prepared above.
Bending strength and impact resistance by Izod were measured according to IS K7113. Also, the bending strength was measured after immersion in carbon tetrachloride, and the retention rate was obtained by comparison with the value in the normal state and used as a measure of solvent resistance. As a result, the results shown in Table 3 below were obtained.

[0040]

[Table 3]

From the results in Table 3 above, it can be seen that the composition according to the present invention has improved impact resistance and solvent resistance.

[0042]

When the thermoplastic resin composition of the present invention is used, the solvent resistance and chemical resistance of the polycarbonate resin can be improved without lowering the impact resistance of the polycarbonate resin.

Claims (2)

[Claims] 1. (a) Polycarbonate resin, (b)
It is selected from the group consisting of a polyester-based polymer, and (c) a polymer block mainly composed of an aromatic vinyl compound and a hydrogenated polybutadiene block obtained by hydrogenating a polybutadiene having a 1,2-bond content of 20% or less. At least one block A, a hydrogenated polyisoprene block, a hydrogenated polybutadiene block obtained by hydrogenating a polybutadiene having a 1,2-bond content of 30 to 70%, and hydrogenated isoprene and butadiene A modified block copolymer having a hydroxyl group at the terminal of a block copolymer containing at least one block B selected from the group consisting of random copolymer blocks (c-
1) and / or at least one polymer block C mainly containing an aromatic vinyl compound and at least one polyisobutylene block D, a modified block copolymer having a hydroxyl group at the terminal ( c-
A resin composition comprising 2). 2. The weight ratio of component (b) to component (c) is (b) / (c) = 98/2 to 45/55, and component (a), component (b) and component ( A thermoplastic resin composition, wherein the total weight ratio of c) is 95/5 to 30/70.