JPH02242843A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having permanently antistatic properties containing a specific amount of a polymer prepared by polymerizing a specific monomer in the presence of a polyalkylene glycol. CONSTITUTION:A thermoplastic resin composition comprising (A) 0-93pts.wt. graft copolymer prepared by polymerizing A2: 90-5pts.wt. monomer consisting of 40-100wt.% aromatic vinyl monomer (preferably styrene) and/or (meth)acrylic acid ester monomer (preferably methyl methacrylate) and 60-0wt.% another copolymerizable vinyl monomer (preferably acrylonitrile) in the presence of A1: 1-80pts.wt. rubber-like polymer (preferably diene-based rubber), (B) 0-93pts.wt. copolymer prepared by polymerizing the same monomer as the component A2 and (C) 7-80pts.wt. polymer prepared by polymerizing 90-5pts.wt. monomer similar to the component A2 in the presence of 10-95pts.wt. polyalkylene glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Denominator] The present invention relates to a thermoplastic resin composition containing a modified polyalkylene glycol polymer and having permanent antistatic properties.

[Conventional technology]

Many synthetic resins are electrical insulators with high surface electrical resistance due to their chemical structure, and therefore static charges easily accumulate on their surfaces during processing and use.

For this reason, these have many practical drawbacks. For example, polystyrene, styrene-acrylonitrile copolymer, high-impact polystyrene, rubber-reinforced styrene-acrylonitrile copolymer (ABS, AES% AAS, A
Since C3) easily becomes dirty and has flakes attached to it, its use as parts of electrical and electronic equipment is restricted. It is known to provide a preventive finish to such molding materials with a band, and a method of kneading polyalkylene glycol as an antistatic agent is well known.

[Problem that the invention seeks to solve]

In a resin composition incorporating polyalkylene glycol, the polyalkylene glycol bleeds out to the surface over time and eventually loses its antistatic performance.

In view of the above-mentioned problems, the present inventors have made extensive studies and found that aromatic vinyl and/or (meth)acrylic acid ester monomers, or other copolymerizable monomers thereof, can be added to polyalkylene glycol in the presence of polyalkylene glycol. The inventors discovered that a composition containing a specific amount of a polymer obtained by polymerizing a vinyl monomer is a long-lasting antistatic composition, and developed the present invention.

[Means for solving problems]

That is, the present invention provides: (c) 40 to 100% by weight of an aromatic vinyl monomer and/or (meth)acrylic acid ester monomer and other copolymers in the presence of 1 to 80 parts by weight of a rubbery polymer; A graft copolymer obtained by polymerizing 99 to 20 parts by weight of a monomer consisting of 60 to 0% by weight of possible vinyl monomers, former aromatic vinyl monomers and/or (meth)acrylic acid ester monomers C) A copolymer obtained by polymerizing 40 to 100% by weight of 40 to 100% by weight of other copolymerizable vinyl monomers, and C) an aromatic vinyl monomer in the presence of a polyalkylene glycol 10 to 95% by weight. 90 to 90% by weight of monomers and/or (meth)acrylic acid ester monomers and 60 to 0% by weight of other copolymerizable vinyl monomers
(iii) 0 to 98 parts by weight, 80 to 93 parts by weight, and (07 to 80 parts by weight) when the total amount of (B and C) is 100 parts by weight.
The object of the present invention is to provide a thermoplastic resin composition having excellent permanent antistatic properties, characterized in that it is composed of parts by weight.

The thermoplastic resin composition of the present invention will be explained in detail below.

-(A) Graft copolymer- The Shikoku graft copolymer contains 100 to 40 parts by weight of aromatic vinyl and/or (meth)acrylic acid ester monomer and It is obtained by polymerizing 99 to 20 parts by weight of a monomer consisting of 0 to 60% by weight of other vinyl monomers copolymerizable with these. If the ratio of the rubbery polymer to the monomer is outside the above range, the physical property balance of the final composition will be poor.
70 parts by weight, and 90 to 30 parts by weight of the monomer.

Aromatic vinyl monomer and/or (meta) monomer
If the weight of the acrylic acid ester monomer is less than 40 π, the processability of the final composition and the appearance of the molded product will be poor. Preferably it is 50 to 10ox amount%.

(c) As the rubbery polymer constituting the side graft copolymer, those having a glass transition temperature of 0'C or lower are suitable, and diene rubbers such as polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and polyisoprene are preferred. , acrylic rubbers such as polychloroprene and butyl polyacrylate, and ethylene-propylene rubbers such as ethylene-propylene rubber and ethylene-propylene-diene rubber. Particularly preferred is diene rubber.

Examples of the aromatic vinyl monomer include styrene, σ-methylstyrene, vinyltoluene, chlorostyrene, and 0-ethylstyrene, and one or more of them can be used. Styrene is particularly preferred.

Examples of the (meth)acrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methyl acrylate, and one or more types can be used. Particularly preferred is methyl methacrylate.

Other vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; Examples include β-unsaturated carboxylic acid monomers, maleimide monomers such as maleimide and N-phenylmaleimide, and one or more types can be used.

Acrylonitrile is particularly preferred.

(A) W14 graft copolymer can be obtained by a known polymerization method. Examples include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and combinations thereof. emulsifier,
There are no particular restrictions on the type of suspending agent, initiator, etc. and the method of adding the monomer, and it is possible to use bulk addition, divided addition, continuous addition, etc.

-(6 copolymer) The fBl copolymer in the present invention contains 100 to 100% of the aromatic vinyl monomer and/or (meth)acrylic acid ester monomer.
40% by weight and 0 to 60% by weight of other copolymerizable monomers, and if the aromatic vinyl monomer and/or acrylic acid ester monomer is less than 40% by weight, the final composition Poor processability and appearance of molded products. Preferably it is 50 to 100% by weight.

In addition, examples of the aromatic vinyl monomer, (meth)acrylic acid ester monomer, and other copolymerizable monomers include the monomers described in the section of the graft copolymer above. Of course, the specific compounds of the monomers used in the fBl graft copolymer and the fBl copolymer do not need to be the same; for example, (c) a graft copolymer using styrene as the aromatic vinyl monomer, Using d-methylstyrene (
It may also be a B4 copolymer.

(There is no particular restriction on the method for producing the a∙ copolymer, and as with the ^1 graft copolymer, various polymerization methods, addition methods, etc. can be used.

10 polymer - The 0 polymer in the present invention is an aromatic vinyl monomer and/or polymer in the presence of 10 to 95 parts by weight of polyalkylene glycol
or (meth)acrylic acid ester monomer 40-100% by weight and other copolymerizable vinyl monomers 60-0% by weight
It is obtained by polymerizing 90 to 5 parts by weight of a monomer consisting of:

If the polyalkylene glycol is less than 10 parts by weight, the antistatic property will not be sufficient, and if it exceeds 95 parts by weight, the modified effect will be weakened, and the antistatic property will be poor due to surface cleaning or aging.

In other words, permanence is lost. Preferably, they are 50 to 90 parts by weight of polyalkylene glycol and 50 to 10 parts by weight of monomer.

Further, the monomers are aromatic vinyl monomer and/or (meth)acrylic acid ester monomer 40 to 100% by weight π and other copolymerizable monomers 60 to 0% by weight. Monomer and/or (meth)acrylic acid ester monomer is 4
If it is less than 0% by weight, the processability of the final composition and the appearance of the molded product will be poor.

Preferably it is 50 to 100% by weight.

Polyalkylene gellicols are made from di- and polyfunctional (cyclo)aliphatic residues and may also contain small amounts of olefinic groups. Examples include di- or polyols, ethylene glycol, 1,2-propylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, mannitol, and one or more alkylene oxides (e.g. ethylene oxide,
propylene oxide), etc., and -
m or two or more types can be used. In particular, polyalkylene glycol containing a 1,2-propylene structure is preferred.

Further, both linear and branched chain polyalkylene glycols can be used, but those with appropriate branching are preferred.

There is no particular restriction on the molecular weight of polyalkylene glycol, but it is 500 to 1.5000, preferably 1000 to 1000.
000, particularly preferably 2000 to 5000.

Along with polyalkylene glycol, aromatic vinyl monomers, (meth)acrylic acid ester monomers, and other copolymerizable monomers that can constitute the (q-polymer) include the above-mentioned (
A) Monomers mentioned in the column of graft copolymers may be mentioned. Of course, it is not necessary that the specific compounds of each monomer used in the tetra-graft copolymer and/or (8-copolymer) and (q-polymer) be the same.

◎There are no particular restrictions on the method for producing the polymer, and as with the graft copolymer, various polymerization methods, addition methods, etc. can be used. In particular, non-aqueous bulk polymerization and solution polymerization are preferred. Furthermore, there are no limitations on the initiator, and examples include commercially available initiators such as diacyl peroxide, perester, dialkyl peroxide, hydroperoxide, aliphatic or araliphatic azo compounds, and one or more types of initiators may be used. Can be used. Particularly preferred are dibenzoyl peroxide, di-t-butyl peroxide, azoisobutyronitrile, and 1,8-bis-(t-butylperoxy-isopropyl)benzene.

In the thermoplastic resin composition of the present invention, the above-mentioned (c)
Graft copolymer, Japanese copolymer and (q polymer total 1
00iffi part, (A) O~98 heavy f1 part, (60
~93 parts by weight and (q 7 to 80 parts by weight.) If the amount of q polymer is less than 7 parts by weight, the antistatic properties will be insufficient, and if it exceeds 80 parts by weight, the final composition will become soft and have poor mechanical properties. Undesirable.

There are no particular restrictions on the method for producing the composition, and (A),
(Kneading can be carried out using a known kneading machine such as a Banbury mixer roll or an extruder, taking into consideration the shape of the mouth and the shape (powder, granule, liquid, etc.)).

In addition, other thermoplastic resins such as polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyamide, polyphenylene ether, etc. can be mixed with the composition of the present invention. In addition, pigments, dyes, lubricants, flame retardants, plasticizers, antioxidants, ultraviolet absorbers,
Not only known additives such as fillers, but also known antistatic agents such as anionic, cationic, nonionic, etc. can be added.

〔Example〕

The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way. In addition, it is based on parts and % persimmon weight.

Reference example 1 ^ Graft copolymer polybutadiene latex (particle size 0.40μ, gel 8
0%) (solid content), 50 parts of a monomer consisting of 70% styrene and 30% acrylonitrile was polymerized based on a known emulsion polymerization method to prepare a graft copolymer.

(a Copolymer) 75 parts of styrene and 25 parts of 7-crylonitrile were polymerized based on a known suspension polymerization method to prepare a copolymer.

0 Polymer C-1 = 1 part of benzoyl peroxide was added to 75 parts of polypropylene glycol (X-1) having a weight average molecular weight of 2000, and 25 parts of methyl methacrylate was added to A over 3 hours at 95 to 100°C in a nitrogen atmosphere. A modified polyalkylene glycol polymer C-1 was prepared by continuous addition and further polymerization at 95 to 100°C for 6 hours.

C-2 = Polymerization was carried out in the same manner as C-1, except that polyethylene glycol (X-2) with a weight average molecular weight of 312,000 was used as the polyalkylene glycol, and polymer c-2
adjusted.

C-3: A block copolymer of ethylene oxide and propylene oxide (Asahi Denka's "Pluronic F68, average molecular weight 88501, ethylene oxide content 1180%)" (X-3) was used as the polyalkylene glycol.
Polymer c-3 was prepared by polymerization in the same manner as in -1.

C-4 = Polymerization was performed in the same manner as c-1, except that the amount of polypropylene glycol was changed to 50 parts, and 35 parts of styrene and 15 parts of acrylonitrile were used instead of methyl methacrylate to prepare polymer C-4. Shit:.

After mixing the various polymers or unmodified polyalkylene glycols prepared in the above-mentioned reference examples at the blending ratio shown in Table 1, the mixture was kneaded using a Banbury-type internal kneader (for 4 minutes,
170-220°C), a molten mixture was obtained. After pelletizing with a roll and cutter, use an injection molding machine (cylinder temperature set at 220°C) to form 60mm x 60mm pellets.
A flat plate of m×3 m+++ was molded, and its antistatic property (surface specific resistance value) was evaluated by the following method.

(1) After molding: Immediately after molding, the surface was washed with isopropyl alcohol and wiped, then the humidity was adjusted at 50% RH and 23° C. for 24 hours, and measurements were taken.

(A: After being left for 150 days: After molding, after being left in 50% RH and 23°C for 50 days while washing with isopropyl alcohol every 10 days, after washing the surface with isopropyl alcohol again and wiping the surface, The humidity was controlled at 5o%RH and 123°C for 24 hours.

As is clear from Table 1, the resin compositions of the present invention (Executive Individuals 1 to 6) all have low surface resistivity,
Moreover, the resistance value does not change much even with surface cleaning or changes over time, and it exhibits excellent permanent antistatic properties.

On the other hand, modified polyalkylene glycol (the amount of q is 7
When the amount is less than parts by weight (Comparative Examples &1 and &2), the antistatic property (resistance value) is poor. In addition, when unmodified polyalkylene gellicol (X) was added (comparative individuals 3 to A5
), the antistatic property (resistance value) deteriorates significantly due to surface cleaning and aging.

〔Effect of the invention〕

The resin composition of the present invention has excellent permanent antistatic properties.

Claims (1)

Scope of Claims: (A) Copolymerization of 40 to 100% by weight of an aromatic vinyl monomer and/or (meth)acrylic acid ester monomer and other copolymers in the presence of 1 to 80 parts by weight of a rubbery polymer. A graft copolymer obtained by polymerizing 99 to 20 parts by weight of a monomer consisting of 60 to 0% by weight of a possible vinyl monomer, (B) an aromatic vinyl monomer and/or a (meth)acrylic acid ester monomer; A copolymer obtained by polymerizing 40 to 100% by weight of a monomer and 60 to 0% by weight of another copolymerizable vinyl monomer, and (C) an aromatic compound in the presence of 10 to 95 parts by weight of polyalkylene glycol 90 to 90% monomers consisting of 40 to 100% by weight of vinyl monomers and/or (meth)acrylic acid ester monomers and 60 to 0% by weight of other copolymerizable vinyl monomers
(A) 0 to 93 parts by weight, (B) 0 to 93 parts by weight, and C) A thermoplastic resin composition comprising 7 to 80 parts by weight.