JPS62100550A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:A composition, obtained by incorporating a composition containing a specific rubber-reinforce styrene resin and a specific aromatic vinyl compound/ maleic anhydride copolymer with an alkylenebisfatty acid amide and having well-balanced heat and impact resistance and moldability. CONSTITUTION:A thermoplastic resin composition obtained by incorporating 100pts.wt. composition, consisting of (A) 5-70wt% thermoplastic resin, prepared by copolymerizing an alkenyl aromatic monomer with an unsaturated dicarboxylic acid anhydride in the presence or absence of a rubber-like polymer having <=0 deg.C glass transition temperature and having 5-50wt% content of the above-mentioned anhydride and (B) 95-30wt% rubber-reinforced thermoplastic resin, obtained by polymerizing 95-40wt% total of an alkenyl aromatic monomer and vinyl cyanide monomer in the presence of 5-60wt% rubber-like polymer and having 0.20-0.70dl/g intrinsic viscosity of a component soluble in methyl ethyl ketone and having 2-30wt% content of the rubber-like polymer with (C) 1-10pts.wt. alkylenebisfatty acid amide expressed by the formula (R<1> and R<3> are >=8C alkylene; R<2> is >=2C alkylene).

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a thermoplastic resin composition with improved impact strength, molding processability, heat resistance and molding thermal stability. More specifically, a copolymer with a specific structure obtained by copolymerizing an alkenyl aromatic monomer and an unsaturated dicarboxylic acid anhydride, a rubber-reinforced thermoplastic resin with a specific structure, and a specific amount of ethylene bis The present invention relates to a thermoplastic resin composition comprising stearylamide.

b. Prior Art As a method for improving the heat resistance of rubber-reinforced styrene resins, a method is generally used in which a part or all of styrene is replaced with α-methylstyrene.

For example, in order to improve the heat resistance of ABS resin, which is a typical rubber-reinforced styrene-based resin, a method using α-methylstyrene as part of the graft monomer, or a graft copolymerization method in which styrene and acrylonitrile are graft-polymerized to polybutadiene. α-methylstyrene for coalescence
Methods of mixing acrylonitrile copolymers are known.

In order for these compositions to obtain higher heat resistance, α
- It is necessary to increase the content of methylstyrene. However, when the content of α-methylstyrene is increased, heat resistance improves, but on the other hand (1) impact strength decreases.

■ Molding processability decreases.

■ Thermal stability decreases.

There are other difficulties.

With the recent diversification of applications, molding materials have high heat resistance,
Impact resistance is required, and as molded products become larger or have more complex structures, I! ii] Thermal stability is required for molding materials.

However, the conventional method of improving heat resistance by using α-methylstyrene in rubber-reinforced styrenic resins has achieved a high level of physical property balance among heat resistance, impact strength, moldability, and thermal stability. It was difficult to maintain the

Problems to be Solved by the C0 Invention As described above, it has been difficult to produce a rubber-reinforced styrenic resin with an excellent balance of heat resistance, impact resistance, and moldability using conventional methods. As a result of intensive studies, the inventors found that a specific amount of alkylene bis fatty acid amide was blended into a resin composition consisting of a specific rubber-reinforced styrene resin and an aromatic vinyl compound-maleic anhydride copolymer with a specific structure. It has been discovered that by doing so, a resin composition with an excellent balance of heat resistance, impact resistance, and moldability can be obtained, and the present invention has been achieved.

Means for Solving the C0 Problem The present invention provides (A) a resinous polymer consisting of an alkenyl aromatic monomer, an unsaturated dicarboxylic acid anhydride, and, depending on the case, a vinyl monomer copolymerizable with these. A copolymer or graft copolymer obtained by copolymerizing a monomer mixture forming a polymer in the presence or absence of a rubbery polymer having a glass transition temperature of 0°C or lower, and A thermoplastic resin having a saturated dicarboxylic anhydride content of 5 to 50% by weight, a rubbery polymer content of 5 to 70% by weight, and (B) a rubber polymer polymer of 5 to 60% by weight. A graft copolymer obtained by polymerizing a total amount of 95 to 40% by weight of monomers consisting of an alkenyl aromatic s-mer, a vinyl cyanide ester, and optionally a methacrylic acid ester m-mer in the presence of , and the intrinsic viscosity of the methyl ethyl ketone-soluble component (matrix resin) of the copolymer (measured at 30°C in methyl ethyl ketone) is 0.20 to
Rubber reinforced thermoplastic resin 95-3 with 0.10 dl/g
(C) alkylene bis fatty acid amide H2 represented by the following formula, based on 100 parts by weight of a resin composition in which the total amount of rubbery polymers in the resin composition is 2 to 30% by weight.
The present invention provides a thermoplastic resin composition characterized in that it contains 21 to 10 parts by weight of No(, -R'-R''-R''-CONH).

The thermoplastic resin (A) used in the present invention contains alkenyl aromatic monomers, unsaturated dicarboxylic acid anhydrides, and in some cases vinyl monomers copolymerizable with these under bulk or solution polymerization conditions. It is obtained by radical copolymerizing 100 to 70 parts by weight of a monomer forming the resinous polymer containing 0 to 30 parts by weight of a rubbery polymer having a glass transition temperature of 0°C or lower.

A preferred copolymerization method is to first dissolve the rubbery polymer in an alkenyl aromatic monomer and, in some cases, a vinyl monomer to be copolymerized with it, and then add a molecular weight regulator and a polymerization solvent as necessary. In addition, in the presence of a radical polymerization initiator, the concentration ratio of the alkenyl aromatic monomer or a mixture thereof with a vinyl monomer and the unsaturated dicarboxylic acid anhydride is kept substantially constant during the polymerization period. Continuously adding unsaturated dicarboxylic acid anhydride to a reaction temperature of 40 to 17
A method of polymerizing at 0°C is used.

The above-mentioned alkenyl aromatic monomers are not particularly limited, but examples include ebastyrene, α-methylstyrene, p-methylstyrene, 0-methylstyrene, nuclear-substituted halogenated styrene, and indene, particularly styrene. is preferred.

In addition, there are no particular limitations on the unsaturated dicarboxylic anhydride.
For example, maleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, phenylmaleic anhydride, aconitic anhydride, etc. can be used, and maleic anhydride is preferred. . Two or more of these alkenyl aromatic monomers and unsaturated dicarboxylic acid anhydrides may be used in combination.

In addition, examples of vinyl monomers copolymerizable with the above-mentioned monomers as optional components include vinyl cyanide compounds such as acrylonitrile and methacrylate trile;
Examples include meth)acrylic acid alkyl esters, and two or more of these can also be used in combination. The content of these vinyl monomers in the thermoplastic resin (A) is 35
It is preferable that the weight is less than or equal to the weight.

The content of unsaturated dicarboxylic acid anhydride is
It is 5 to 50% by weight of A), preferably 10 to 35% by weight. If it is less than 5% by weight, the heat resistance and impact resistance of the finally obtained resin composition will not be sufficiently improved. Moreover, if it exceeds 50% by weight, the fluidity of the resin composition finally obtained and the thermal stability during molding will be significantly reduced.

Examples of rubbery polymers having a glass transition temperature of 0°C or lower include butadiene-based rubbery polymers containing butadiene as a main component (for example, butadiene homopolymer rubber, styrene-butadiene copolymer rubber, butadiene-(meth)acrylic acid copolymer rubber, polymer rubber, acrylonitrile-butadiene copolymer rubber),
Chloroprene rubber polymer, isoprene rubber polymer, natural rubber, chlorinated polyethylene, ethylene-propylene copolymer rubber, ethylene-diene copolymer rubber, cycloolefin rubber polymer etc. can be mentioned.

In addition, the proportion of the rubbery polymer in the thermoplastic resin (A) is
If the amount exceeds 30% by weight, the viscosity of the polymerization solution becomes extremely high, making it difficult to carry out polymerization in practice.

The preferable intrinsic viscosity of the thermoplastic resin (8) (measured at 30°C in methyl ethyl ketone, the same applies hereinafter) is 0.35 to 0.
It is 60. When the intrinsic viscosity is less than 0.35, the impact strength decreases, and as a result, the strength of the weld portion of a practical molded product tends to decrease. On the other hand, if it exceeds 0.60, molding processability tends to deteriorate, which is not preferable.

The rubber-reinforced thermoplastic resin (B) used in the present invention contains 5 to 60% by weight of a rubbery polymer component, an alkenyl aromatic monomer, a vinyl cyan monomer, and optionally: 9 (, It is a graft copolymer consisting of 95 to 40% by weight of a monomer mixture component consisting of a methacrylic acid ester monomer.

The rubber-reinforced thermoplastic resin (B) of the present invention can be obtained by graft copolymerizing the above-mentioned monomer components in the presence of the rubbery polymer, as long as the rubbery polymer and monomer components are in the above-mentioned ranges. Method for producing a graft copolymer ■ A method for producing a graft copolymer having the above-mentioned composition range by blending a graft copolymer and a copolymer consisting of the above-mentioned monomer components. It can be anything.

The grafting ratio of the graft copolymer constituting the resin (R) is preferably 20 to 120%, more preferably 30 to 120%, in terms of impact resistance, molding thermal stability, and heating dimensional stability.
It is 100%. Here, the grafting rate is determined by the following formula.

The intrinsic viscosity of the matrix resin contained in the resin (B) is from 0.20 to 0.70°, preferably from 0.25 to 0.45, from the viewpoint of impact resistance and heating dimensional stability. If the intrinsic viscosity is less than 0.20, a product with excellent heat resistance and impact resistance cannot be obtained, while if it exceeds 0.70, moldability deteriorates, which is not preferable.

As the rubbery polymer, alkenyl aromatic monomer, vinyl cyanide monomer, and methacrylic acid] to stellate compounds, the compounds listed in the above-mentioned thermoplastic resin (A) are used. Preferred compounds are also the same as those shown therein.

The rubber-reinforced thermoplastic resin (A) can be produced by any of the following methods: emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and a combination of these polymerization methods.

The intrinsic viscosity of the matrix resin can be adjusted by a generally known method, for example, by suitably controlling the polymerization temperature and the amount and type of the molecular weight regulator and polymerization initiator.

The composition ratio of thermoplastic resin (A)/rubber-reinforced thermoplastic resin (B) is 5/95 to 70/30, preferably 10% by weight.
/90 to 60/40.

If the resin (A) is less than 5% by weight, the heat resistance will be low, while if it exceeds 70% by weight, the moldability will be 1 and the impact resistance will be low. This is not preferable because it reduces performance.

The content of the rubbery polymer in the resin composition consisting of resin (A) and resin (B) is 5 to 30% by weight, preferably 10 to 2% by weight.
It is 5% by weight. If it is less than 5% by weight, the impact resistance will be low, while if it exceeds 30% by weight, the impact resistance and moldability will be poor, which is not preferable.

The alkylene bis fatty acid amide (C) is at least one selected from compounds represented by the following general formula.

H2NOC-R'R"-R3-CONH2 In the above formula, the carbon number of R1 and R3 is preferably 10 to 20, more preferably 7 or 16 to 20. Also, R2
The number of carbon atoms is preferably 2 to 8, more preferably 2.
-4, particularly preferably 2. Particularly preferred as such a compound is ethylene bisstearylamide.

The alkylene bis fatty acid amide is used in the resin composition 10 mentioned above.
1 to 10 parts by weight, preferably 1°5 to 0 parts by weight
5 parts by weight is blended.

By blending the alkylene bis fatty acid amide in the above range, it is possible to significantly improve the impact resistance and moldability without lowering the heat resistance of the resin composition. Better heat resistance than other compositions,
A resin composition having a balance of impact resistance, moldability, and heat resistance stability can be obtained. If the alkylene bis fatty acid amide is less than 1 part by weight, the desired effects of the present invention cannot be obtained, while if it exceeds 10 parts by weight, the heat resistance and impact resistance will deteriorate, which is not preferable.

Conventional methods can be used to mix the components of the composition of the invention. For example, after mixing each component in a mixer, the mixture is melt-kneaded in an extruder at 200 to 280°C to form 4'' granules.

To make it even easier, each component is directly melted and kneaded in a molding machine.

It can be molded by

The compositions of the invention include antioxidants such as 2,6-di-t,-butylene-4-methylphenol, 2-(1-methylcyclohexyl-4,6-dimethylphenol,
2,2'-methylene-bis-(4-ethyl-6-t
-butylphenol), 4.4' -thiobis=(6
-t-butyl-3-methylfer)-l), dilaurylthiodipropionate, tris(di-nonylphenyl)
phosphites, waxes; ultraviolet absorbers, e.g. p-t
-butylphenyl salicylate, 2゜2' -dihydroxy-4-methoxybenzophenone, 2- (2'
--hydroxy-4'-n-octoxyphenyl)benzotriazole; lubricants such as paraffin wax,
Stearic acid, hydrogenated oil, stearamide, methylene bisstearamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride; flame retardants such as antimony oxide, aluminum hydroxide, zinc oxalate, Tricresyl phosphate, tris(dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane,
Hexabromobenzene, tetrabromobisphenol A
; antistatic agents, such as stearamidopropyl dimethyl-β-hydroxyethylammonium nitrate; colorants, such as titanium oxide, carbon black; fillers, such as calcium carbonate, clay, silica, glass fibers, glass spheres, carbon fibers; Pigments and the like can be added as necessary.

The composition of the present invention may also contain other thermoplastic resins such as styrene resins, polyphenylene ethers, polyamides, acrylic resins, and polyesters.

The composition of the present invention can be used for automobile parts, electrical appliances, household goods,
It can be suitably used for various industrial supplies.

e. Examples Next, the present invention will be explained in more detail with reference to Examples.

Note that the thermoplastic resin (A) and rubber-reinforced thermoplastic resin (B) used in this example were manufactured by the following method.

[Method for producing thermoplastic resin (A)]

Styrene-unmentioned 7-[,-4ji''UU1buttons
(denoted as T/gate A H (1)) 850 g of styrene was placed in a stainless steel reactor equipped with a stirring device.
400 g of methyl ethyl ketone and 2 g of benzoyl peroxide were charged. After replacing the internal air with nitrogen,
Warm water (90°C) was placed in the jacket and heated.

When the internal temperature of the reactor reached 50° C., maleic anhydride and methyl ethyl ketone were added for 12 hours at the following rate using a variable amount continuous addition device.

A solution of maleic anhydride was added at a rate of 215+n6/hour for 2 hours, then at a rate of 96 m6/hour for 3 hours, then at a rate of 5
Add at a rate of 7mf/hour for 5 hours, then continue for 3 hours until the addition is complete.
0ml! / Added at the speed of time. After the addition of the maleic anhydride solution was completed, stirring was continued for 2 hours while keeping the internal temperature at 90°C. The polymerization conversion rate was 85%. The copolymerized amount of maleic anhydride in the polymer was 15.7% by weight.

After polymerization, 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) was added as an antioxidant.
5 g was added, followed by removal of residual monomer and solvent under reduced pressure and drying.

Steele 2 two-member woodworker, one car and one car (hereinafter referred to as ST)
/ M A R (2)) Stirring device a) 758 g of styrene and 400 g of methyl ethyl ketone were placed in a stainless steel reactor, 2 g of benzoyl peroxide was added while stirring, and the air inside was replaced with nitrogen.
Warm water (90°C) was placed in the jacket and heated. When the internal temperature of the reaction vessel reached 50°C, maleic anhydride 2
A solution consisting of 20 g and 800 g of methyl ethyl ketone,
Additions were made using a variable flow continuous device at the following rates:

791ml of maleic anhydride solution! /Add 30 minutes at the speed of an hour, then next! : Added for 2 hours at a speed of 1 m217 m 6 / hour, added for 3 hours at a speed of 75111 β / hour,
Further addition was continued at a rate of 29 mff/hour until the addition was complete.

After the addition of the anhydrous maleic acid solution was completed, stirring was continued for 2 hours while keeping the internal temperature at 90°C. The polymerization conversion rate was 90%. The copolymerized amount of maleic anhydride in the polymer was 24.6%. After the polymerization was completed, 5 g of 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) was added as an antioxidant, and then the residual monomer and solvent were removed under reduced pressure and the mixture was dried.

Styrene - Anhydrous E4 Ai Z Fuji 1 Kafujimawari (hereinafter referred to as ST/MA former 3) In a stainless steel reactor equipped with a stirring device, 520 g of styrene,
490 g of maleic anhydride, 4000 g of methyl ethyl ketone
g.

2 g of benzoyl peroxide was charged. After replacing the internal air with nitrogen, pour hot water (90°C) into Jaquela 1-.
was added, heated, and reacted for 5 hours. Polymerization conversion rate is 99
%Met. The copolymerized amount of maleic anhydride in the polymer is 4
It was 7.5% by weight.

After polymerization, 2.2'-methylene- is added as an antioxidant.
Bis-(4-methyl-6-t-butylphenol) 5g
was added, followed by removal of residual monomer and solvent under reduced pressure and drying.

Styrene, two-membered ice, and one-kilogram (hereinafter referred to as ST/M^H (4)) 950 g of styrene in a stainless steel reactor with a stirring device,
60g maleic anhydride, 4000g methyl ethyl ketone
.

2 g of benzoyl peroxide was charged. After replacing the air inside with nitrogen, hot water (90°C) was poured into the jacket and heated to cause a reaction for 7.5 hours. Polymerization conversion rate is 84
%Met. The copolymerized amount of maleic anhydride in the polymer is 5
．． It was 0% by weight. After polymerization, 2
．． 5 g of 2'-methylene-bis-(4-methyl-6-t-butylphenol) was added, and then the remaining particles and solvent were removed under reduced pressure and the mixture was dried.

[Production method of rubber reinforced thermoplastic resin (B)] 1゜ Production method average particle size of graft copolymers G-1, G-2, G-3 2
26 parts of a 300-person polybutadiene latex, 4 parts of a styrene-butadiene copolymer latex with a bound styrene content of 25% by weight, containing 65% of particles with an average particle size of 4400 Å or more, 52 parts of styrene, 18 parts of acrylonitrile, disproportionated 100% aqueous soap solution containing 2.0 parts of potassium rosinate
parts, t-=F bodecylcaptan 1.0 parts, 10 parts of an aqueous solution containing 0.005 parts of ferrous sulfate, and 50 parts of an aqueous solution containing 0.35 parts of sodium pyrophosphate and 0.25 parts of dextrose. The mixture is charged into a sealed pressure-resistant container, the system is purged with nitrogen, and the temperature of the system is raised to 70° C. with thorough stirring, and then 0.4 part of cumene hydroperoxide is added to initiate polymerization. After 3 hours, the resulting polymer latex was taken out, mixed with 1.0 part of 2.2'-methylene-bis-(4-methyl-6-t-butylphenol) in an emulsified state, coagulated with sulfuric acid, washed, and dehydrated. A white powdery ABS G-1 was obtained by drying. Polymerization was carried out in the same manner as in (B4) using 0.8 part of t-dodecyl mercaptan for G-2 and 0.7 part of t-dodecyl mercaptan for G-3. The properties of the obtained resin are shown below.

G-I G-2G-3 Rubber polymer content (χ) 30 30
Intrinsic viscosity of 30 matrix 0.25 0.32
0.38 graph ratio (χ)
52 58 632, Production method of graft copolymer G-4 In the polymerization method of G-1, 52 parts of polybutadiene latex with an average particle size of 2300 Å and a bound styrene content of 25% containing 65% particles with a particle size of 4400 Å or more. Styrene-butadiene copolymer late Nox 8 parts by weight, 24 parts styrene
．． Polymerization was carried out in the same manner as G-1, except that 6 parts of acrylonitrile, 15.4 parts of acrylonitrile, and 0.5 parts of t-dodecyl mercaptan were used, and a gelabt copolymer G-1 having the following characteristics was obtained.
I got 4.

Rubber content (1) 60 Intrinsic viscosity of matrix 0.5 Graft ratio (χ) 453, Production method of graft copolymer G-5 In the polymerization method of G-1, t-4 decyl mercaptan was added to 1 G-5 was obtained by using .5 parts and carrying out an 11-g combination under the same conditions as G-1.

Rubber content (χ) 30 Intrinsic viscosity of 7 trix 0.18 Graft ratio (X) 4B Examples 1 to 12/Comparative Examples 1 to 6 The components shown in Table 1 were mixed in a 50 mm extruder, Created a beret.

Using these pellets, the melt flow rate (measurement conditions 220 'C11C11
O was measured.

In addition, the pellet is made using a 5oz injection molding machine (Toshiba l5425A
) to create a test piece and measure the Izod impact strength (A
STM D256 i thickness 'A'', notched 23℃),
Heat distortion temperature (ASTM D648; thickness 'A', 2
64psi, 23°C).

The results are shown in Table-1.

The results of each Example and Comparative Example are evaluated based on Table 1.

Examples 1 to 12 are resin compositions within the scope of the present invention, and the physical properties targeted by the present invention are obtained.

Comparative Examples 1 to 6 are as follows.

Comparative Example 1: This is an example in which ethylene bisstearylamide, which is component (C) of the present invention, is not used, and moldability and impact resistance are poor.

Comparative Example 2: This is an example in which ethylene bisstearylamide, component (C) of the present invention, was used beyond the scope of the present invention, and the heat resistance and impact resistance were poor.

Comparative Example 3: This is an example in which the intrinsic viscosity of 71-lysox, component (B) of the present invention, is less than the range of the present invention, and the heat resistance and impact resistance are poor.

Comparative Example 4: In some cases, the intrinsic viscosity of the matrix of component (B) of the present invention exceeded the range of the present invention, and moldability was poor.

Comparative Example 5: This is an example in which methylene bisstearyl amine t', which is outside the range of component (C) of the present invention, is used, and the impact resistance is poor.

Comparative Example 6: This is an example in which the rubber content in the composition of the present invention exceeds the range of the present invention, and the heat resistance and moldability are poor.

r0 Effects of the Present Invention The thermoplastic resin composition of the present invention has an excellent balance of physical properties among impact resistance, heat resistance, and moldability, and is an excellent resin material that can meet recent strict quality requirements.

Claims (2)

[Claims] (1) (A) A monomer mixture forming a resinous polymer consisting of an alkenyl aromatic monomer, an unsaturated dicarboxylic acid anhydride, and, in some cases, a vinyl monomer copolymerizable with these, A copolymer or graft copolymer obtained by copolymerization in the presence or absence of a rubbery polymer having a glass transition temperature of 0°C or lower, and having an unsaturated dicarboxylic anhydride content of 5 to 50 Thermoplastic resin whose rubbery polymer content is 0 to 30% by weight 5 to 7
0% by weight, and (B) a monomer consisting of an alkenyl aromatic monomer, a vinyl cyan monomer, and optionally a methacrylic acid ester monomer in the presence of 5 to 60% by weight of the rubbery polymer. A graft copolymer obtained by polymerizing a total amount of 95 to 40% by weight, and the intrinsic viscosity of the methyl ethyl ketone-soluble component of the copolymer (measured at 30 ° C. in methyl ethyl ketone) is 0.20 to 0. .70dl/
(C) with respect to 100 parts by weight of a resin composition consisting of 95 to 30% by weight of a rubber-reinforced thermoplastic resin of 95 to 30% by weight, and in which the total amount of rubbery polymers in the resin composition is 2 to 30% by weight. Alkylene bis fatty acid amide H_2NOC-R^1-R^2-R^3-CONH_2
In the formula, R^1 and R^3 are linear or branched alkylene groups having 8 or more carbon atoms, and R^1 and R^3 may be the same or different, and R^2 is a group having 2 carbon atoms. A thermoplastic resin composition comprising 1 to 10 parts by weight of the above linear or branched alkylene group. (2) The intrinsic viscosity of the matrix resin (B) is 0.25
The resin composition according to claim (1), which has a water content of 0.45 dl/g.