JPH0297558A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition excellent in impact resistance, moldability, etc., by mixing nylon 6 with two specified graft copolymers and two aromatic vinyl copolymers in a specified weight ratio. CONSTITUTION:Nylon 6 (A) having a ratio of the terminal amino to the terminal carboxyl <=0.9, a graft copolymer (B) obtained by copolymerizing 10-100wt.% aromatic vinyl monomer (e.g., styrene) with 90-0wt.% copolymerizable vinyl monomer in the presence of a rubberlike polymer, a graft copolymer (C) obtained by further adding 0.1-50wt.% vinyl monomer having reactivity with and an affinity for nylon 6 in the production of component B, a copolymer (D) containing 10-100wt. % aromatic vinyl monomer and a copolymer (E) containing 10-99.9wt. % aromatic vinyl monomer and 0.1-50wt.% vinyl monomer reactive with nylon 6 are prepared. 5-90 pts.wt. component A, 90-0 pts.wt. components B and/or D and 0.1-95 pts.wt. component E are mixed with each other in such an amount that the total of components A to E is 100 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a composite thermoplastic resin composition of nylon-6 and styrene resin, which has excellent impact resistance and moldability.

<Conventional technology> Nylon-6 resin has excellent moldability, heat resistance, mechanical strength, chemical resistance, abrasion resistance, etc., so it is widely used in mechanical parts, electrical/electronic parts, and automobile parts. There are, but
Questions include a decrease in notched impact strength in dry conditions and dimensional changes due to moisture absorption. On the other hand, high impact polystyrene (HIPS), which is a rubber-reinforced styrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), and ABS resin in which the rubber component of ABS resin is replaced with ethylene-propylene rubber or acrylic rubber and A
AS resins are also widely used in automobile parts, electrical equipment parts, office equipment parts, etc., and although they have excellent impact resistance and dimensional stability, they have the problem of relatively poor chemical resistance.

Nylon-6 and AB
It has been proposed to melt and mix styrene resins such as S resin (Japanese Patent Publication No. 38-28476, etc.);
It is known that the compatibility between 6 and styrene resin is poor, resulting in molded products showing delamination and only materials with low impact strength being obtained.

In order to improve the compatibility between nylon-6 and styrene-based resins, it has been proposed to introduce and modify functional groups such as carboxylic acid and amide groups that have reactivity or affinity with nylon-6 into ABS-based resins. (Japanese Unexamined Patent Publication No. 54-11159,
JP-A-58-32656, JP-A-58-93745, etc.)
However, although impact strength and delamination are improved by introducing functional groups, the problem arises that flowability is significantly reduced due to increase in molecular weight or crosslinking due to reaction with nylon-6.

<Problems to be solved by the invention> The present inventors have discovered that nylon-6-styrene-based nylon-6
The inventors have discovered that a material that is reactive with nylon-6 and has extremely excellent impact resistance and moldability can be obtained, and the present invention has been achieved.

<Means for Solving the Problems> That is, the present invention provides nylon-6 having a ratio of 0.9 or less;
Weight% and other copolymerizable vinyl monomers: 90-0
A graft copolymer obtained by copolymerizing monomers consisting of 1% by weight, ◎ 1 aromatic vinyl monomer in the presence of a rubbery polymer.
0 to 99.9% by weight, 0.1 to 50% by weight of vinyl monomers having reactivity or affinity with nylon-6, and 89.9 to 0% by weight of other copolymerizable vinyl monomers. A graft copolymer obtained by copolymerizing monomers consisting of 0 to 100% by weight of an aromatic vinyl monomer and 90 to 0% by weight of other copolymerizable vinyl monomers. (1) 10 to 99.9% by weight of an aromatic vinyl monomer, 0.1 to 50% by weight of a vinyl monomer having reactivity or affinity with nylon-6, and other copolymerizable materials. The total amount of (A), (B), (C), (D) and (E) is 100 times the total amount of (A), (B), (C), (D) and (E). By weight, (A) 5 to 90 parts by weight, (B
) and/or (D) in a ratio of 90 to 0 parts by weight and (C) and/or (E) in a ratio of 0.1 to 95 if 1 part to provide a material with extremely excellent impact resistance and moldability. It is something.

Hereinafter, the present invention will be explained in detail.

The terminal amino group was measured by titration with 0.01N hydrochloric acid (the same applies hereinafter).

The degree of polymerization is not particularly limited, and the relative viscosity of concentrated sulfuric acid (polymer 11 is dissolved in 98% concentrated sulfuric acid, measured at 25°C, the same applies hereinafter) is within the range of 1.0 to 6.0. Things can be used.

As the polymerization method, melt polymerization, interfacial polymerization, solution polymerization, anionic polymerization, bulk polymerization, solid phase polymerization, and a combination of these methods are used, and among these methods, melt polymerization is preferred.

Other nylons that can be mixed or copolymerized include ethylene diamine, diaminobutane, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine,
, 2.4- and 2゜4.4-trimethylhexamethylene diamine, 1.3 and 1,4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexyl)
Aliphatic, cyclic, and aromatic diamines such as methane, metaxylylene diamine, and paraxylylene diamine, and aliphatic, cyclic, and aromatic diamines such as adipic acid, speric acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid. Nylon derived from group dicarboxylic acids; so-called -
Nylon obtained by ring-opening polymerization of lactams such as caprolactam and ω-dodecalactam, nylon derived from 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc., nylon copolymerized with these, and mixed nylon. Examples include.

- The ratio of amino groups exceeds 0.9. ), nylon 12, nylon 46, nylon 66, nylon 610 and their copolymers, even nylon 6/66 ("
10 mark means it is a copolymer), nylon 6
Useful materials include Nylon 6/610, Nylon 6/12, Nylon 66/12, Nylon 6/66/610/12, and mixtures thereof. Also useful are bis(p-aminocyclohexyl)methane/terephthalic acid/isophthalic acid based polyamides.

There are no restrictions on the molecular structure of polyamide, and either linear polyamide, branched polyamide, etc. may be used. Linear polyamide is produced by conventional methods,
Branched polyamide is polymerized by adding a small amount of a branching agent having three or more functional groups capable of forming a polyamide, such as Tamaruba bis((IJ-aminohexyl)amine, diethylenetriamine, trimesic acid, or bislactam) to the raw material. Polymerization method Methods such as melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and combinations of these methods are used.
Melt polymerization is most suitable for boat fishing. Further, particularly when the polyamide raw material is a lactam, the polymer may be obtained by anionic polymerization.

The rubbery polymers used in the graft copolymer 0 in the present invention include diene rubbery polymers such as polybutadiene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, ethylene-propylene copolymers, ethylene Examples include non-diene rubbery polymers such as -propylene-nonconjugated diene copolymer, acrylic rubbery polymer, and chlorinated polyethylene, and one or more types can be used. These rubbery polymers are produced by emulsion polymerization, solution polymerization, bulk polymerization, suspension 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 the particle size is 0.1 to 1 μm and the gel content is 0 to 95%.
It is preferable that

Examples of aromatic vinyl 111ff include styrene, a
-Methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, a
- Methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromustyrene, dibromustyrene, vinylnaphthalene, etc. are exemplified, and - a dish or two or more types can be used.

Other vinyl monomers that can be copolymerized with the aromatic vinyl monomer include vinyl cyanide monomers such as acrylonitrile, methacrylatetrile, fumaronitrile, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2 - Methacrylic acid ester monomers such as ethylhexyl methacrylate, lauryl methacrylate, and cyclohexyl methacrylate, acrylic acid ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, maleimide , N-phenylmaleimide, N-cyclohexylmaleimide and the like are exemplified, and one or more types of each can be used.

Graft copolymer (2) is made from 10 to 100% by weight of an aromatic vinyl monomer and 90 to 0% by weight of other copolymerizable vinyl monomers in the presence of the rubbery polymer (b-1). It can be obtained by copolymerizing monomer (b-2).

There is no particular restriction on the ratio of the rubbery polymer (b-1) to the monomer (b-2) in the graft copolymer ①, but the ratio of the rubbery polymer (b-1) to 20 to 80% by weight, Monomer (
b-2) It is preferably 80 to 20% by weight.

The composition of monomer (b-2) is preferably 30 to 100% by weight of aromatic vinyl monomers and 70 to 0% by weight of other vinyl monomers.

The graft copolymer (C) in the present invention is a vinyl monomer that is basically the same as the graft copolymer (B) but has a functional group that is reactive or has an affinity for nylon-6. The difference is that it has been modified by

The graft copolymer Ω has a functional group that is reactive or has an affinity with the aromatic vinyl monomer 10 to 99.9% by weight of nylon-6 in the presence of the rubbery polymer (c-1). It is obtained by copolymerizing a monomer (c-2) consisting of 0.1 to 50% by weight of a vinyl monomer and 89.9 to 0% by weight of another vinyl monomer.

There is no particular restriction on the ratio of the rubbery polymer (C-1) to the monomer (c-2) in the graft copolymer ρ, but 20 to 80% by weight of the rubbery polymer (C-1), Monomer (
, C-2) is preferably 80 to 20% by weight.

In addition, the composition of @mer (c-2) is 30 to 99.9% by weight of aromatic vinyl monomers and 0 vinyl monomers having functional groups reactive or affinity with nylon-6. .1 to 20% by weight and other vinyl monomers O to 69.9% by weight (
-).

In addition, the rubbery polymer (c
-1) As the aromatic vinyl monomer and other vinyl monomers, the same ones as those exemplified in the section of graft copolymer can.

Vinyl monomers with functional groups that are reactive or have an affinity for nylon-6 include carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid (anhydride). glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxylic acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3
．． 4-epoxybutene, 3,4-epoxy-3-methyl-
1-butene, 3.4-epoxy-1-pentene, 3.4
- Those containing epoxy groups such as dipoxy-1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, p-glycidylstyrene, aminoethyl acrylate , propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate,
Alkyl ester derivatives of acrylic acid or methacrylic acid such as phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methacrylamine and N
-Allylamine derivatives such as methylallylamine, acrylamide derivatives such as acrylamide and N-methylacrylamide, those having amino groups such as p-aminostyrenes, 2-vinylpyridine, 4-vinylpyridine, 5-ethyl-2- Vinylpyridine such as vinylpyridine, 2-methyl-5-vinylpyridine, ■-vinyl-2-pyrrolidone, 3-vinyl-2-pyrrolidone, 1
-vinyl-3-methyl-2-pyrrolidone, 1-vinyl-
Examples include vinylpyrrolidones such as 4-methyl-2-pyrrolidone and 1-vinyl-5-methyl-2-pyrrolidone, vinylimidazole, and the like, and each can be used alone or in combination of two or more.

In the present invention, the copolymer is produced by copolymerizing a monomer consisting of 10 to 100% by weight of an aromatic vinyl monomer and 90 to 0% by weight of another copolymerizable vinyl monomer. However, in particular aromatic vinyl monomer 15-1
00% by weight and other copolymerizable vinyl monomers 85
A copolymer consisting of 0 to 0 nails is preferred.

Incidentally, the monomers used in copolymer 0 are the same as those exemplified in the section of graft copolymer ①, and each can be used alone or in combination of two or more.

Copolymer (2) in the present invention is basically the same as copolymer (P), except that it is modified with a vinyl-based It support having a functional group that is reactive or has an affinity for nylon-6. different.

Copolymer (E) is an aromatic vinyl monomer of 10 to 99.9
% by weight, from 0.1 to 50% by weight of vinyl II-mer having a functional group reactive or affinity with nylon-6 and 89.9 to 0% by weight of other vinyl monomers that can be copolymerized. It is obtained by copolymerizing monomers such as 15 to 999% by weight of aromatic vinyl monomers, nylon-6
0.1 to 20% by weight of a vinyl monomer having a functional group reactive with or having an affinity for other vinyl claws 84.9
Copolymers consisting of ~0% by weight are preferred.

The aromatic vinyl monomer and other copolymerizable vinyl monomers used in the copolymer (E) are the same as those exemplified in the section of the graft copolymer (B).・In addition, as a vinyl monomer having a functional group reactive or affinity with nylon-6, are the same as those exemplified in the section of the graft copolymer (C), and each can be used alone or in combination of two or more.

In addition, graft copolymers (B), (C) and copolymers (
If the composition of each of D) and (E) is outside the range shown above, the impact resistance and moldability of the final composition will decrease.

Graft copolymers (B), (C) and copolymers (D)
, (E) are known emulsion polymerization,
Suspension polymerization, solution polymerization, bulk polymerization, or a combination of these methods is used.

In the present invention, nylon-6 (A), graft copolymer (B), graft copolymer (C), copolymer (D),
The mixed composition of copolymer (E) is (A), (B), (C)
, (D) and (E) as 100 parts by weight,
(A) 5 to 90 parts by weight, preferably 10 to 80 parts by weight,
(B) and/or (D) 90 to 0 parts by weight, preferably 80 to 0 parts by weight, (C) and/or (E) 0.
1 to 95 heavy debt parts, exceeding 100%, or Gelabut copolymer (C
) and/or copolymer (E) in an amount exceeding 95 parts by weight or less than 0.1 parts by weight, the thermoplastic resin composition of the present invention has extremely good impact resistance and moldability. Unable to achieve balance.

Nylon-6 (A), graft copolymer (B), (C
) and the copolymers (D) and (E) are mixed in any order, and the following methods are exemplified.

(1) Simultaneous mixing of all ingredients at once.

After premixing nylon-6 (A) and graft copolymer (C) and/or copolymer (E), the graft copolymer (B) and/or copolymer (D) are mixed.

(3) After premixing the graft copolymer (C) and/or copolymer (E) and the graft copolymer (B) and/or copolymer (D), nylon-6 (A) is mixed. .

Also, there are no restrictions on the form of the mixture, such as latex, powder, pellets, etc.

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

In addition, when mixing, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, dyes, pigments, plasticizers, flame retardants, mold release agents, glass fibers, metal fibers, carbon fibers,
Thermoplastic resins such as polyphenylene oxide, polymethyl methacrylate, polyvinyl chloride, etc. such as metal flakes can also be blended.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these Examples.

Ratio 0.5 Concentrated sulfuric acid relative viscosity 2.8 Ratio 1.5
Concentrated sulfuric acid Relative viscosity 2.8 [Reference Example 1] Preparation of graft copolymer (B)-1: Polybutadiene latex (PBDE) 50 with an average particle size of 0.4 μ and a gel content of 82% was placed in a reactor purged with nitrogen. (solid content) and 100 parts of pure water were charged. 68°C after adding 0.3 part of potassium persulfate
A monomer solution consisting of 15 parts of acrylonitrile, 35 parts of styrene and 0.25 parts of tertiary dodecyl mercaptan, and 20 parts of an emulsifier aqueous solution containing 2.0 parts of potassium rosinate and 0.05 parts of sodium hydroxide were added. Each was added continuously over 465 hours. Thereafter, the temperature of the polymerization system was raised to 70°C, and the mixture was aged for 3 hours to complete the polymerization.

B-2: Ethylene-propylene-ethylidene norbornene copolymer (EPDM, iodine value 21, Mooney viscosity 1
An AES graft copolymer was prepared by a known solution polymerization method.

B-3: In the presence of 50 parts (solid content) of cross-linked polybutyl acrylate latex (PBA) with an average particle size of 0.3 μm, 15 parts of acrylonitrile and 35 parts of styrene were copolymerized by emulsion polymerization to obtain an AAS graft copolymer. A polymer was created.

An acrylamide-modified graft copolymer latex consisting of 2 to 6 parts of acrylonitrile and 5 parts of acrylamide was prepared by an emulsion polymerization method according to JP-A-58-9.3745.

After adding graft copolymers B-1, B-8 and 2 parts of C-lisnonylphenyl phosphite, salting out was performed using magnesium sulfate, and the mixture was separated and recovered. Graft copolymer B-2 was separated and recovered after precipitation in methanol.

[Reference Example] Preparation of copolymer (D)-1: After 120 parts of pure water and 0.3 parts of potassium persulfate were charged into a reactor purged with nitrogen, the temperature was raised to 68°C while stirring. Then 30 parts of acrylonitrile, 7 parts of styrene
A mixed monomer solution consisting of 0 parts and 0.3 parts of t-dodecyl mercaptan and 30 parts of an emulsifier aqueous solution containing 2.0 parts of potassium rosinate and 0.05 parts of sodium hydroxide were each continuously added over 5 hours. , then the polymerization system was heated to 70°C.
The temperature was raised to 1, and the polymerization was completed by aging for 3 hours.

After salting out using calcium chloride, it was separated and collected.

[Reference Example 4] Preparation of copolymer (E) E-1 to E-3 = Copolymer was prepared in the same manner as copolymer (D) except that the composition of the mixed monomer was changed as shown in Table 2. Polymer (E)
It was created.

E-4: A maleic anhydride-modified copolymer was created by a solution polymerization method using benzoyl peroxide as an initiator and methyl ketone as a solvent ◇ Copolymers E-1 to E-3 were prepared using calcium chloride as a salt After analysis, it was separated and collected. Copolymer E-
4 was separated and recovered after precipitation into methanol.

〔Example〕

Nylon-6 (A), the graft copolymers (B), (C), and copolymers (D), (E) prepared in the reference example were
The mixtures were mixed at the proportions shown in the table, and melt-mixed and granulated using a twin-screw extruder with a diameter of 40 mm.

Note that the granulation temperature was set at 250°C. Obtained shellfish
The physical properties of the resin composition were determined by the following method, and the results are shown in Table 3.

・Moldability (flowability): Koka type flow tester (Shimadzu Corporation) 250°C, 60Ky, frLt 7min ・Impact strength (notched Izot): ASTM D-2
56.23°C,' Kg·cm/cm The above test piece for quality evaluation was molded using a 3.5-ounce injection molding machine with the cylinder temperature set at 250°C.

[Examples 1 to 5, Comparative Examples 1 to 4] The influence of the type and amount of nylon-6 on quality will be shown.

[Examples 6-7, Comparative Examples 5-6] Examples using various graft copolymers will be shown.

[Examples 9 to 11, Comparative Example 7] Examples using (graft) copolymers modified with various functional groups will be shown.

(1) PBDEΦ...Polybutadiene (2) EPDM...Ethylene-propylene-ethylidene norbornene copolymer (3) PBA...Polybutyl acrylate
Table 2 Table 3 ＼ ＼ ＼ ＼ ＼ ゝ＼、 ＼、 ＼＼ ＼、 ＼ ＼ <Effects of the Invention> The thermoplastic resin composition of the present invention has excellent impact resistance and moldability, and is suitable for various It has extremely high practical value as a material for industrial parts.

Claims (1)

Scope of Claims: (A) Nylon-6 in which the ratio of terminal amino groups to terminal carboxyl groups is 0.9 or less; (B) aromatic vinyl monomer 10-10 in the presence of a rubbery polymer; A graft copolymer obtained by copolymerizing a monomer consisting of 100% by weight and 90 to 0% by weight of another copolymerizable vinyl monomer; (C) In the presence of a rubbery polymer, an aromatic 10 to 99.9% by weight of a vinyl monomer, 0.1 to 50% by weight of a vinyl monomer having reactivity or affinity with nylon-6, and other copolymerizable vinyl monomers 89. A graft copolymer obtained by copolymerizing monomers consisting of 9 to 0% by weight, (D) 10 to 100% by weight of an aromatic vinyl monomer and 90 to 90% of other copolymerizable vinyl monomers. (E) 10-99.9% by weight of an aromatic vinyl monomer, and 0.1-99.9% by weight of a vinyl monomer having reactivity or affinity with nylon-6. (A), (B), (C), (D) and ( The total amount of E) is 100 parts by weight, (A) 5 to 90 parts by weight, (B)
and/or (D) 90 to 0 parts by weight and (C) and/
or (E) a thermoplastic resin composition mixed in a proportion of 0.1 to 95 parts by weight.