JPH0388842A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent chemical resistance and impact resistance by blending a saturated polyester resin with rubber reinforced styrene-based resin and a specific epoxy modified copolymer in a specific ratio. CONSTITUTION:(A) A saturated polyester resin is blended with (B) a rubber- reinforced styrene-based resin prepared by copolymerizing B1: 50-90wt.% aromatic vinyl-based monomer with B2: 10-50wt.% vinyl cyanide monomer and B3: 0-40wt.% another copolymerizable vinyl-based monomer, (C) an epoxy modified copolymer comprising 50-89.9wt.% B1, 10-49.9wt.% B2, 0-39.9wt.% B3 and C1: 0.1-20wt.% ethylene-based unsaturated epoxy group-containing monomer and (D) a styrene-based copolymer comprising 20-90wt.% B1, 10-50wt.% B2 and 0-70wt.% B3 in the ratio to give 90-10 pts.wt. A, 90-10 pts.wt. B+C and 0-80 pts.wt. C to give a composition comprising 5-40wt.% rubber-like polymer and >=0.001wt.% C1 in the composition.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to a thermoplastic resin having excellent chemical resistance and impact resistance (notched isot) made of a polyester resin, a rubber-reinforced styrene resin, and an epoxy-modified copolymer. This invention relates to a resin composition.

<Prior art> Polystyrene, styrene-acrylonitrile copolymer,
Styrenic resins such as ABS resin, EPDM=rubber, acrylic rubber as a rubber component, AAS resin, and AAS resin have an excellent balance of physical properties and dimensional stability, and are used in a wide range of fields. Among them, there are many applications in the automobile field, but in this case gasoline resistance,
Resistance to chemicals such as brake oil became a problem, and improvements in this aspect were an important issue. On the other hand, saturated polyester resin is already known as a polymer with excellent chemical resistance, but due to its poor impact resistance, saturated polyester resin
It has been proposed to incorporate S resin (Special Publication No. 1973-
80421, Special Publication No. 5l-25261). However, such a resin composition has a problem in that sufficient impact resistance cannot be obtained.

Means for Solving Problems〉 As a result of intensive study on improving the above-mentioned quality problems of compositions made of saturated polyester resins and styrene resins, the present inventors have found that saturated polyester resins, styrene resins and The inventors have discovered that a thermoplastic resin composition with excellent chemical resistance and impact resistance (notched isot) can be obtained by mixing a specific epoxy-modified copolymer in a specific ratio, and has thus arrived at the present invention.

That is, the present invention provides aromatic vinyl monomer 5 in the presence of (A) a saturated polyester resin and (B) a rubbery polymer.
Rubber-reinforced styrenic resin copolymerized with monomers consisting of 0 to 90% by weight, 10 to 50% by weight of vinyl cyanide monomer, and 0 to 40% by weight of other copolymerizable vinyl monomers, 0 aromatic vinyl monomer 50 to 89.9% by weight, vinyl cyanide monomer 10 to 49.9% by weight, ethylenically unsaturated epoxy group-containing monomer o, 1 to 20% by weight and Epoxy-modified copolymer consisting of 0 to 39.9% by weight of other polymerizable vinyl monomers, 20 to 90% by weight of aromatic vinyl monomers, 10 to 50% by weight of vinyl cyanide monomers % and other copolymerizable vinyl monomers from 0 to 70% by weight, and the total amount of (A), (B), (C) and (D) is 100 parts by weight. (A) 90 to 10 parts by weight, (B
)+lC'190-10 parts by weight, (Dl.

~80 parts by weight, and the total composition contains 5 to 40% by weight of the rubbery polymer and at least 0.001% by weight of the ethylenically unsaturated epoxy group-containing monomer. The present invention provides a thermoplastic resin composition characterized by the following.

The present invention will be explained in detail below.

Examples of the saturated polyester resin (A) used in the present invention include polyethylene terephthalate, polybutylene terephthalate, and polyester-ether block polymers having a polyester hard segment and a polyether soft segment, and l,4-butanediol and terephthalic acid. Alternatively, it is synthesized from dimethyl terephthalate and ethylene glycol. Note that these can be used alone or in a mixture of two or more.

In the present invention, the rubber-reinforced styrenic resin contains 50 to 90% by weight of an aromatic vinyl monomer in the presence of a rubbery polymer.
It is produced by polymerizing monomers consisting of 10 to 50% by weight of a vinyl cyanide monomer and 0 to 40% by weight of another copolymerizable vinyl monomer.

Examples of rubbery polymers include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, acrylic acid ester copolymer, and chlorinated copolymer having a glass transition temperature of 0°C or lower. Examples include polyethylene, which can be used alone or in combination of two or more. These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and the like. There are no particular restrictions on the particle size and gel content of the rubbery polymer when produced by emulsion polymerization, but
Average particle size 0, 1-1 μm and gel content 0-95%
It is desirable that

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene,
p-methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromstyrene, dibromstyrene, vinylnaphthalene, etc., and the cyanized vinyl monomers include acrylonitrile, Examples include methacrylatetrile and fumaronitrile, each of which can be used alone or in combination of two or more. Among them, styrene, α-methylstyrene, and acrylonitrile are preferred.

Other copolymerizable monomers include unsaturated alkyl carboxylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and 2-ethylhexyl methacrylate. Examples include ester monomers and imide monomers such as maleimide, N-phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide, each of which can be used alone or in combination of two or more.

If the monomer composition is outside the above range, the compatibility between the rubber-reinforced styrene resin (B) and the epoxy-modified copolymer q will be poor, resulting in a decrease in impact strength when mixed with the saturated polyester resin (6).

There is no particular restriction on the ratio of the rubbery polymer to the monomer, but the rubbery polymer may be 20 to 80% by weight and the monomer may be 80 to 80% by weight.
The content is preferably 20% by weight. There is also no particular restriction on the grafting rate, but it is preferably 20-100%. As the graft polymerization method, a known method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, or a combination thereof can be used.

The epoxy-modified copolymer ◎ used in the present invention contains 50 to 89.9% by weight of aromatic vinyl monomer, 10 to 39.9% by weight of vinyl cyanide monomer, and ethylenically unsaturated epoxy group. It is produced by polymerizing monomers consisting of 0.1 to 20% by weight of a monomer and 0 to 39.9% by weight of another copolymerizable vinyl monomer. Particularly preferred are aromatic vinyl monomers of 59.9 to 80% by weight, vinyl cyanide monomers of 19.9 to 40% by weight, and ethylenically unsaturated epoxy group-containing monomers of 0.1 to 15% by weight. %.

If the composition of the monomer is outside the above range, the compatibility with the rubber-reinforced styrene resin (B) will be poor, which is not preferable.

The aromatic vinyl monomer, vinyl cyanide monomer, and other copolymerizable vinyl monomers constituting epoxy-modified copolymer 0 include the above-mentioned rubber-reinforced styrene resin (B). Those exemplified in the section above can be mentioned, and each can be used alone or in a mixture of two or more, but styrene, α-methylstyrene and acrylonitrile are preferred, and α-methylstyrene and acrylonitrile are particularly preferred. The unsaturated epoxy monomer is a monomer having one or more each of one or more polymerizable unsaturated bonds and one or more epoxy groups in the molecule. Such unsaturated epoxy monomers include, for example, unsaturated glycidyl represented by the general formula % (where R represents a hydrocarbon group having a polymerizable ethylenically unsaturated bond). Esters and unsaturated glycidyl ethers represented by the general formula (R is the same as that of the formula CI, X is a divalent group represented by -CH2-0- or -())) and general Examples include epoxy alkenes represented by the formula (where R is CI), where R' is hydrogen or a methyl group.

Specifically, glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itacones, mono-, di- and triglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-bicyclo[2.2・1] Mono- and diglycidyl esters of hept-5-ene-2,3-dicarboxylic acid (trade name nadic acid), endo-cis-bicyclo[2.2.1) hept-5-ene-2-methyl- Mono- and diglycidyl esters of 2,3-dicarboxylic acid (trade name methylnadic acid), mono- and diglycidyl esters of allylsuccinic acid, glycidyl esters of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene −
p-glycidyl ether or p-glycidyl styrene, 3,4-epoxy-1-butene, 3,4-epoxy-
3-methyl-■-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene,
Examples include 5,6-epoxy-1-hexene and vinylcyclohexene monoxide.

As a method for producing the epoxy-modified copolymer C), known methods such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, or a combination thereof are used. There are also no particular restrictions on the method of adding the ethylenically unsaturated epoxy group-containing monomer, such as mixing it with other monomers and adding it to the polymerization system;
A method of adding it as an aqueous solution is used.

Furthermore, there is no particular restriction on the molecular weight of the epoxy modified copolymer C), but preferably the weight average molecular weight is 10.0.
00 to 1,000,000.

The styrenic copolymer 0 in the present invention includes 20 to 90% by weight of aromatic vinyl monomers and 1% by weight of vinyl cyanide monomers.
It is produced by copolymerizing 0 to 50% by weight and 0 to 70% by weight of another copolymerizable vinyl monomer. Examples of aromatic vinyl monomers, vinyl cyanide monomers, and other copolymerizable vinyl monomers include those exemplified in the section of the rubber-reinforced styrenic resin (B), and each It can be used alone or in combination of two or more, but in particular styrene, α-methylstyrene, acrylonitrile,
N-phenylmaleimide and methyl methacrylate are preferred.

Specifically, styrene-acrylonitrile copolymer, α
- methylstyrene-acrylonitrile copolymer, styrene-α-methylstyrene-acrylonitrile copolymer,
Styrene-acrylonitrile-methyl methacrylate copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α-methylstyrene-acrylonitrile-N-phenylmaleimide copolymer, styrene-acrylonitrile-N-phenylmaleimide-methyl methacrylate copolymer Examples include α-methylstyrene-acrylonitrile-N-phenylmaleimide-methyl methacrylate copolymer.

The above-mentioned saturated polyester resin (
The composition ratio of A), rubber-reinforced styrenic resin (B), epoxy modified copolymer q, and styrenic copolymer ρ) is 90 to 10 parts by weight per 100 parts by weight of the total,
(B) + (C) 90 to 10 parts by weight, (DIO to 80 parts by weight).

Outside this range, the excellent balance between chemical resistance and impact resistance that characterizes the thermoplastic resin composition of the present invention cannot be achieved.

Preferably (6) 15 to 70 parts by weight, (B) +085 to
30 parts by weight, and 00 to 60 parts by weight.

In particular, it consists of 60-85% by weight of α-methylstyrene, 0-20% by weight of styrene, 15-40% by weight of vinyl cyanide monomer, and 0-25% by weight of other copolymerizable vinyl monomers. It is preferable from the viewpoint of impact resistance and heat resistance that 5 to 60 parts by weight of styrene copolymer 0 be blended.

Also, 20 to 60% by weight of aromatic vinyl monomer, 10 to 40% by weight of vinyl cyanide monomer, and 5 to 5% of imide monomer.
65% by weight and other copolymerizable vinyl monomers (excluding imide monomers).

5 to 6 styrenic copolymer 0 to 50% by weight
It is preferable from the viewpoint of heat resistance that the amount is 0 parts by weight.

In addition, in the present invention, the content of the rubbery polymer and the ethylene-based unsaturated epoxy polymer in the composition is important, and if the rubbery polymer content in the total composition is less than 5% by weight, the impact strength will decrease. But again.

If it exceeds 40% by weight, moldability will deteriorate, which is not preferable.

Preferably it is 5 to 30% by weight. If the amount of the ethylenically unsaturated epoxy group-containing monomer is less than 0.001% by weight, it is not preferable because the compatibility with the saturated polyester resin (A) is poor. Preferably it is 0.1% by weight or more.

There are no restrictions on the mixing order or state of the saturated polyester resin (A), rubber-reinforced styrenic resin (B), epoxy-modified copolymer C), and styrenic copolymer 0, and pellets, beads, powder, etc. Depending on the form (
Examples of A) include simultaneous mixing of four components (uniform, ◎, and 0), and a method in which specific components are premixed and then other components are mixed.

As a mixing method, a known method such as a Banbury mixer roll or an extruder can be employed.

In addition, antioxidants, ultraviolet absorbers,
Additives such as light stabilizers, antistatic agents, lubricants, dyes, pigments, plasticizers, flame retardants, mold release agents, glass fibers, metal fibers, carbon fibers, metal flakes, reinforcing materials, and fillers can be added. In addition, polyacetal, polycarbonate, polyamide,
Thermoplastic resins such as polyphenylene oxide, polymethyl methacrylate, and polyvinyl chloride may also be appropriately blended.

Next, the present invention will be specifically explained using reference examples, working examples, and comparative examples, but the present invention is not limited by these in any way. Note that all parts and percentages are expressed on a weight basis.

Reference example 1 Polyester resin (A) A-1: Polyethylene terephthalate (PET) RY-
560 Toyobo A-2 = Polybutylene terephthalate (PBT) N −
1000 Mitsubishi Rayon Co., Ltd. A-3: Polybutylene terephthalate) (PBT)N
-1200 manufactured by Mitsubishi Rayon Co., Ltd. Reference Example 2 Rubber-reinforced styrenic resin)-1: By emulsion polymerization in the presence of 60 parts (solid content) of polybutadiene latex with an average particle size of 0.45μ and a gel content of 83%. , 12 parts of acrylonitrile, and 28 parts of styrene were copolymerized to produce an ABS graft copolymer latex (grafting rate: 35%, intrinsic viscosity of free acrylonitrile-styrene copolymer: 0.88). Note that the intrinsic viscosity was measured in dimethylformamide at 30°C.

(Unit: 100 mg/l: ABS graft copolymer latex consisting of 50 parts of polybutadiene, 15 parts of acrylonitrile, and 35 parts of styrene in the same manner as B-1 (grafting ratio 55%, intrinsic viscosity of free acrylonitrile-styrene copolymer 0) .58) was produced.

AAS graft copolymer was obtained by copolymerizing 15 parts of acrylonitrile and 35 parts of styrene by an emulsion polymerization method in the presence of 50 parts (solid content) of B-3 crosslinked polybutyl acrylate latex with a two-average particle diameter of 0.3μ. A latex (grafting ratio 50%, free acrylonitrile-styrene copolymer intrinsic viscosity 0.63) was produced.

B-4: AES graft copolymer (graft ratio 52%, free acrylonitrile-styrene copolymer with an intrinsic viscosity of 0.60) was produced by a solution polymerization method.

Graft copolymers B-1 to B-3 are each used as an antioxidant per 100 parts of latex solid content in Sumilizer NW.
After adding 1 part of trisnoryl phenyl phosphite and 2 parts of trisnoryl phenyl phosphite, salting out was performed using magnesium sulfate, followed by separation and recovery. Graft copolymer B-4 was separated and recovered after precipitation in methanol.

Reference Example 3 Epoxy modified copolymer 0 C-1: After charging 120 parts of pure water and 0.3 parts of potassium persulfate into a reactor purged with nitrogen, the temperature was heated to 65°C with stirring.
The temperature rose to . Thereafter, a mixed monomer solution consisting of 30 parts of acrylonitrile, 65 parts of styrene, 5 parts of glycidyl methacrylate, and 0.3 parts of t-dodecylmercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of sodium dodecylsulfonate were each continuously added over 5 hours. The polymerization system was heated to 70°C and aged for 3 hours to complete the polymerization, producing a copolymer with an intrinsic viscosity (in dimethylformamide, 30°C) of 0.56.

c-2: 30 parts of acrylonitrile in the same manner as c-1,
A copolymer having an intrinsic viscosity of 0.53 was prepared from 65 parts of α-methylstyrene and 5 parts of glycidyl methacrylate.

C-3: 23 parts of acrylonitrile in the same manner as C-1,
A copolymer having an intrinsic viscosity of 0.68 was prepared from 52 parts of α-methylstyrene and 25 parts of glycidyl methacrylate.

Each epoxy modified copolymer was separated and recovered after salting out using calcium chloride.

Reference Example 4 Styrenic Copolymer 0 Copolymers D1 to D5 having the following compositions were produced in the same manner as c-1.

STY: Styrene AMS: α-methylstyrene ACN: Acrylonitrile N-PMI: N-phenylmaleimide MMA: Methyl methacrylate Styrenic copolymers D-1 to D-5 were separated and recovered after salting out using magnesium sulfate. .

Examples and Comparative Examples The saturated polyester resin (A), rubber-reinforced styrenic resin (B), epoxy-modified copolymer q, and styrene-based copolymer 0 shown in the reference example were mixed in the composition shown in Table 1. The mixture was melt-mixed and granulated using a 40 m twin-screw extruder.

Note that the granulation temperature was set at 250'C.

The physical properties of the obtained resin composition were measured by the following method, and the results are shown in Table 2.

Impact strength (notched isot): ASTMD-
256 (23°C) Chemical resistance: Each piece of a 150mm x 20+uX arm molded product was fixed to a chibari jig, subjected to a deflection of 80 trm, and then immersed in various chemicals for 24 hours to determine the presence or absence of cracks.

The above test pieces for quality evaluation were molded using a 3.5 ounce injection molding machine with the cylinder temperature set at 250'C.

<Examples 1 to 6.17 to 18, Comparative Examples 1 to 3> The effects of epoxy modified copolymer C) are shown.

In addition, the effect when an α-methylstyrene copolymer is used as the zero component will be shown.

<Examples 7-8, Comparative Example 4> Effects when using various saturated polyesters (A) will be shown.

<Examples 9-11, Comparative Examples 4-5> The influence of the amount of saturated polyester (A) is shown.

<Examples 12 to 14> The effects of using various rubber-reinforced styrene resins will be shown.

<Examples 15-16, Comparative Example 6> The influence of the amount of rubber in the total composition is shown.

<Example ■ 9-21〉 Maleimi A carbon-based copolymer was used as the zero component. This shows the effect of the case.

Claims (1)

[Claims] 1. (A) a saturated polyester resin; (B) an aromatic vinyl monomer 5 in the presence of a rubbery polymer;
Rubber-reinforced styrenic resin copolymerized with monomers consisting of 0 to 90% by weight, 10 to 50% by weight of vinyl cyanide monomer, and 0 to 40% by weight of other copolymerizable vinyl monomers, (C) Aromatic vinyl monomer 50-89.9% by weight
, vinyl cyanide monomer 10 to 49.9% by weight, ethylenically unsaturated epoxy group-containing monomer 0.1 to 20% by weight
and (D) an epoxy-modified copolymer consisting of 0 to 39.9% by weight of other copolymerizable vinyl monomers, and (D) 20 to 90% by weight of aromatic vinyl monomers, and vinyl cyanide monomers. A styrenic copolymer consisting of 10 to 50% by weight of vinyl monomer and 0 to 70% by weight of other copolymerizable vinyl monomer, and the sum of (A), (B), (C) and (D). (A) 90 to 10 parts by weight, assuming the amount is 100 parts by weight,
(B) + (C) 90 to 10 parts by weight, (D) 0 to 80 parts by weight, and the rubbery polymer in the total composition is 5 to 40% by weight, ethylene-based A thermoplastic resin composition comprising an unsaturated epoxy group-containing monomer in a proportion of at least 0.001% by weight.