JPH07316421A - Permanently antistatic composite resin molding - Google Patents

Abstract

PURPOSE:To prepare a composite resin molding with a good permanent antistatic property by dispersing a polyurethane phase in a stripe form in the surface layer portion of a composite of a thermoplastic resin and a polyurethane having a polyoxyethylene chain. CONSTITUTION:A thermoplastic resin (A) is melt-kneaded together with a polyurethane (B) having a polyoxyethylene chain to disperse a part of the phase B in a stripe form in the surface layer portion of the resultant composite resin. The polyurethane (B) has four or more repeated polyoxyethylene chains and may be prepared in the resin (A) in a molten state by polymerizing an active hydrogen-contg. polyfunctional compd. (such as polyethylene glycol) and polyisocyanate, either the polyfunctional compd. or the polyisocyanate having a polyoxyethylene chain. Polyolefins and thermoplastic styrene resins are pref. used as the resin (A). The resin (A) content is 60 to 95wt.%, and the polyurethane (B) has a polyoxyethylene chain content of 5 to 40wt.% (pref. 5 to 20wt.%) and a mol.wt. of 6000 to 2000. A shear of not less than 10<2>sec<-1> is applied to the composite to provide the phase B dispersed in a stripe form in the surface layer portion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a permanent antistatic composite resin molded article and a method for antistatically charging a resin molded article.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting antistatic properties to a resin, a method of adding a surfactant having a polyhydric alcohol fatty acid ester as a main component (Japanese Patent Publication No. 6-21198, Japanese Patent Publication No. 43104, etc.). )It has been known.

However, these methods have a problem in the durability of the antistatic property such that the antistatic property disappears when washed with water.

[0004]

The present inventors have arrived at the present invention as a result of intensive studies to obtain a composite resin molded article having good permanent antistatic properties and resin properties.

That is, the present invention comprises a composite of a thermoplastic resin (A) and a polyurethane (B) having a polyoxyethylene chain, and at least a part of the (B) phase is dispersed in a streak form at the surface layer of the composite resin. And a permanent antistatic composite resin molded product. And the active hydrogen-containing polyfunctional compound (B-1) and polyisocyanate (B-2) in the melted (A)
At least a part of the (B) phase is applied to the composite resin surface layer by applying at least 10 ² sec ^{-1 to} the composite obtained by polymerizing the above or the composite obtained by melt-kneading (A) and (B). This is a method of permanently preventing static charge of a molded body in which stripes are dispersed at a portion.

As (A) in the resin composition of the present invention,
Examples thereof include (co) polymers of vinyl compounds, polyesters, polyamides, polyimides, and thermoplastic resins such as poly (thio) ethers.

Of these, vinyl compounds constituting the (co) polymer of vinyl compounds include olefins (ethylene, propylene, butene-1, isobutene, 4-methylpentene-1, octene, etc.); aromatic vinyl Hydrocarbons or their substitution products (styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, vinyltoluene, etc.); (meth) acrylic acid and its alkyl (C 1-18) esters (methyl acrylate) , Ethyl acrylate, butyl acrylate, methyl methacrylate, etc.); vinyl ether (methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, etc.); vinyl alcohol derivative (vinyl acetate, vinyl butyrate, etc.); (meth) acrylonitrile; (meth) acrylic Bromide and N-substituted derivatives thereof;
Dienes (butadiene, isoprene, etc.); halogen-substituted compounds of ethylene (vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylidene fluoride, etc.); unsaturated polycarboxylic acids (maleic acid, fumaric acid, etc.) or their anhydrides, halogens Compounds, alkyls (C1-C1
8) Examples include esterified products.

Examples of polymers or copolymers of these vinyl compounds include polyolefin thermoplastic resins [polyethylene, polypropylene, ethylene-α-olefin copolymer (ethylene-propylene copolymer, ethylene-butene-1 Copolymers, etc.), olefin-diene copolymers (EPDM, etc.), ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, chlorinated polypropylene, maleic acid-modified polypropylene, etc.] Thermoplastic resins (polystyrene, ABS resin, AS resin), polyacrylic acid, polymethylmethacrylate, polyacrylonitrile, polyacrylamide, polyvinyl alcohol, polyvinyl acetate, polybutadiene, polyvinyl chloride, polytetrafluoroethylene, etc. You can

As the polyester, aromatic polyesters [polymers of aromatic dicarboxylic acid esters (polyethylene terephthalate, polybutylene terephthalate,
Polycondensation products of bisphenol A with terephthalic acid and / or isophthalic acid, etc.), polycondensation products of paraoxybenzoic acid, etc.]; Aliphatic polyesters [Polymers of aliphatic dicarboxylic acid esters (polybutylene adipate, polyethylene adipate, etc.)] Etc.]; polycarbonate; and a co-polycondensation product of an alkylene oxide (polyethylene glycol, polypropylene glycol, etc.) with a compound constituting two or more kinds of these, or a compound constituting these polymers.

As the polyamide, 6-nylon, 6,
6-nylon, 6,10-nylon, 11-nylon,
12-nylon, 4,6-nylon, etc. and these 2
Examples thereof include a co-amidated compound of at least one kind, and a copolycondensate of a compound forming the polymer with a compound forming the polyester or an alkylene oxide (polyethylene glycol, polypropylene glycol, etc.).

As the polyimide, pyromellitic acid and 1,
Examples thereof include polycondensates with 4-diaminobenzene and the like; copolycondensates of compounds forming polyimide with the compounds forming the polyamide, that is, polyamideimide.

Examples of the poly (thio) ether include polyphenylene ether, polyoxymethylene, polyether ether ketone, polyphenylene sulfide, polysulfone and the like, and co-etherified products of two or more of these.

Among these thermoplastic resins (A), preferred are (co) polymers of vinyl compounds, particularly polyolefin type thermoplastic resins and styrene type thermoplastic resins.

The above examples of the thermoplastic resin (A) can be used in combination of two or more kinds.

The molecular weight of this thermoplastic resin (A) is usually 1
10,000 to 7,000,000, preferably 10.0
It is 00 to 3,000,000. Molecular weight is 10,000
If it is less than 0 or exceeds 7,000,000, molding becomes difficult and it is not practical.

The amount of the thermoplastic resin (A) is 60 to 9
It is 5% by weight, preferably 80 to 95% by weight. 60
If it is less than 95% by weight, the mechanical strength will be poor.

The melting temperature of (A) is 80 ° C. or higher, preferably 100 ° C. or higher. If the melting temperature is less than 80 ° C, the heat resistance is poor and it is not practical.

In the present invention, the active hydrogen-containing polyfunctional compound (B-1) and / or polyisocyanate (B-
Examples of those having a polyoxyethylene chain in 2) include polyethylene glycol, ethylene oxide propylene oxide block copolymers (pluronic type ethylene oxide propylene oxide copolymers, etc.),
Both-end modified polyethylene glycol (both-end diamine type polyethylene glycol, both-end glycidyl polyethylene glycol, both-end isocyanate type urethane prepolymer containing polyethylene glycol as a component, etc.) Both-end modified ethylene oxide propylene oxide block copolymer (both-end diamine type) Ethylene oxide propylene oxide block copolymer, glycidyl ethylene oxide propylene oxide block copolymer at both ends, ethylene oxide propylene oxide block copolymer 1
Both ends isocyanate type urethane prepolymer as a component) and the like.

The polyoxyethylene chain means a chain in which oxyethylene is repeated by 4 or more chains. Those having an oxyethylene chain of less than 4 do not exhibit the antistatic function in the permanent antistatic composite resin composition obtained in the present invention. More preferably, it is 4 or more and 70 or less. Those having more than 70 chains are good in terms of permanent antistatic property,
It may reduce the resin properties. This will be described more specifically. For example, when polyethylene glycol (hereinafter referred to as PEG) is used as (B-1), PEG-400, PEG-1000, and P in the range of 4 to 70 chains are used.
Molded articles using EG-2000 and the like show good permanent antistatic properties and resin properties, but molded articles using only triethylene glycol, which has three chains, have insufficient permanent antistatic properties. Further, the molded product using only PEG-6000 having more than 70 chains has good permanent antistatic property but does not have sufficient boiling water resistance.

The total amount of polyoxyethylene chains in (B) is 5-40% by weight, preferably 5-20% by weight. If it is less than 5% by weight, the antistatic property becomes insufficient, and
If it exceeds the weight%, the resin properties become insufficient, which is not preferable. Examples of the active hydrogen-containing polyfunctional compound (B-1) having no polyoxyethylene chain, which is optionally used in the production of (B) in the present invention, include low molecular weight diols [ethylene glycol, propylene glycol,
1,4-butanediol, 1,6-hexanediol, etc.]; polyether diol [alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above-exemplified low molecular weight diols (however, the number of ethylene oxide added is 4 (Less than a chain), ring-opening polymer of alkylene oxide (polytetramethylene glycol, etc.)]; polyester diol [aliphatic dicarboxylic acid (adipic acid, maleic acid, dimerized linoleic acid, etc.) or aromatic dicarboxylic acid (phthalic acid, terephthalate) Acid, etc.) with a low molecular weight diol exemplified above, a polylactone diol, etc. by ring-opening polymerization of ε-caprolactone]; diamines (isophoronediamine, 4,4′-diamino-3,3′-dimethyl) Dicyclohexyl meta Amine, polyetherdiamine, etc.); trivalent or higher alcohols (trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher amines (diethylenetriamine, triethylenetetramine, etc.); amino alcohols (triethanolamine, etc.); And an active hydrogen-containing urethane prepolymer obtained by reacting the above-mentioned active hydrogen-containing compound with the following polyisocyanate.

Examples of the polyisocyanate (B-2) having no polyoxyethylene chain, which is optionally used in the production of (B) in the present invention, include aromatic diisocyanates (tolylene diisocyanate, xylylene diisocyanate, naphthyl). Diisocyanate, diphenylmethane diisocyanate, etc., alicyclic diisocyanate (isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, diisocyanate methylcyclohexane, etc.), aliphatic diisocyanate (hexamethylene diisocyanate, etc.), trifunctional or higher polyisocyanate [triphenylmethane Triisocyanate, tris (isocyanate phenyl) thiophosphate, hexamethylene diisocyanate Cyclic trimer, etc.], and (except those with the proviso the polyoxyethylene chain) isocyanate group-containing urethane prepolymer obtained by the reaction of these with the active hydrogen-containing compound and the like.

Two or more kinds of these compounds having at least two active hydrogens and polyisocyanate may be used in combination.

At this time, the ratio of isocyanate group to active hydrogen is 1: 2 to 2: 1, the terminal group may be either an isocyanate group or active hydrogen, and the terminal isocyanate group is a compound having one active hydrogen. There is no problem with the blockade.

The molecular weight of (B) in the permanent antistatic resin molding obtained in the present invention is usually 6,000 to 500,000.
It is 0. Molecular weight less than 6,000 or 500,0
If it exceeds 00, the permanent antistatic property is not sufficiently exhibited.

There is no problem even if these active hydrogen-containing polyfunctional compounds having polyoxyethylene chains and / or polyisocyanates are mixed with other polymerizable functional group-containing compounds.

In the present invention, a dispersant may be present in the composite resin molded product in order to assist the dispersion of the respective constituent components.

The preferred dispersant (C) is
When the thermoplastic resin (A) is a polyolefin, it is a polyolefin having active hydrogen, a (anhydrous) carboxylic acid group, or a carboxylic acid halide group, or a copolymer-based dispersant of polyolefin and polyurethane. Of these, preferred are hydroxyl group-, epoxy group-, and acid anhydride group-containing polyolefins. More specific examples include hydroxyl group-modified polyolefin and maleic anhydride graft-modified polyolefin. When (A) is polystyrene, preferable (C) is a styrene (co) polymer containing a hydroxyl group, an epoxy group, and an acid anhydride group. More specific examples thereof include a styrene-hydroxyethyl methacrylate copolymer, a styrene-glycidyl methacrylate copolymer, and a styrene-maleic anhydride copolymer. The resin properties of the molded product containing these dispersants (C) are improved. When (A) is an aromatic polyester, a polycarbonate, a polyamide, a polyimide, a polyamideimide, a polyacetal, a polyphenylene oxide, a polyether ether ketone, a polyphenylene sulfide, and a polysulfone, a styrene maleic anhydride copolymer, an SBS resin, a SEBS resin, Terminal amino type and /
Alternatively, a carboxylic acid type polyamide oligomer, a terminal carboxylic acid type and / or a hydroxyl group type polyester oligomer and the like are mainly used.

The number average molecular weight of (C) is usually 800-
3,000,000, preferably 1,000-200,
It is 000. If it is less than 800, the physical properties of the resin of the molded product are poor, and if it is 300,000 or more, the effect of adding (C) cannot be obtained.

When the dispersant (C) is used, the proportion of (C) is usually 0.0 with respect to the total weight of (A) and (B).
It is 5 to 50%, preferably 0.1 to 20%.

The composite resin composition of the present invention is usually obtained by melt-kneading (A) and (B) prepared in advance from (B-1) and (B-2). In the melted (A) (B
It can also be obtained by polymerizing -1) and (B-2). In this case, the polymerization can be carried out in the presence of (D). The temperature for carrying out these is usually in the range of 10 to 350 ° C, preferably 80 to 230 ° C.

The reaction pressure is not particularly limited, but when industrial production is considered, it is usually reduced pressure (0.1 mmHg) to 50 atm, preferably reduced pressure (0.1 mmHg) to 30 atm.

(B) is usually produced by subjecting (B-1) and (B-2) to a urethanization reaction in advance, and the reaction temperature is in the range of 30 to 230 ° C., preferably 40 to
It is 200 ° C.

The reaction pressure is not particularly limited, but in view of industrial production, it is usually reduced pressure (0.1 mmHg) to 10 atm, preferably reduced pressure (0.1 mmHg) to 5 atm.

During this reaction, a solvent and a catalyst can be used if necessary. The solvent to be used may be a known solvent for urethanization reaction having no active hydrogen, and examples thereof include dimethylformamide, methyl ethyl ketone and toluene. The catalyst to be used may be one known as a catalyst for urethanization reaction, and examples thereof include organometallic compounds such as dibutyltin dilaurate and dioctyltin dilaurate, and amines such as triethylamine and diazabicycloundecene. .

Examples of the reaction vessel include various known mixers such as extruders, kneaders and Banbury mixers.

In the present invention, it is necessary to disperse at least a part of the phase (B) in the form of streaks in the surface portion of the composite resin in an amount of 10 ² s
It is necessary to apply a shear of ec ^-1 or more. Shear 10
If it is less than ² sec ^-1 , sufficient streaky dispersion cannot be obtained in the surface layer portion, and the antistatic property is poor. For imparting shear, various known molding machines such as an injection molding machine, an inflation molding machine, an extrusion molding machine, a blow molding machine, and a spinning machine can be used.

The molded product of the present invention includes containers, cases,
It is suitable for bumpers, hoses, films and various housing materials.

[0038]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples indicate parts by weight. The evaluation of the molded articles described in Examples and Comparative Examples was performed by the following methods. (1) Impact strength: ASTM D256 (notched, 3.2 mm thick) (2) Flexural modulus: ASTM D790 (3) Surface specific resistance value: injection molded 2 mm thick test piece was used to measure the super insulation 20 ℃, humidity 5
It was measured in a 0% RH atmosphere. The surface resistivity was evaluated by subjecting the test piece to the treatment and conditioning described below and measuring the surface resistivity. (A) Unwashed with water: after molding, the test piece is kept at 20 ° C.
Leave for 24 hours in an atmosphere of 50% humidity RH. (B) Washing with water: After molding, the test piece was washed with a detergent (Mama Lemon;
After washing with an aqueous solution of Lion Co., Ltd., followed by thorough washing with ion-exchanged water, the surface water is dried and removed, and then left in an atmosphere of 20 ° C. and a humidity of 50% RH for 24 hours. The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, part means part by weight.

Example 1 Polypropylene [UBE-Polypro J manufactured by Ube Industries, Ltd.]
609H, abbreviated as PP hereinafter; corresponding to thermoplastic resin (A)] 80 parts, PEG2000 manufactured by Sanyo Chemical Industry Co., Ltd. [number average molecular weight 2,000; active hydrogen-containing polyfunctional compound (B)
-1)] and 17.8 parts of diphenylmethane diisocyanate [hereinafter abbreviated as MDI; corresponding to polyisocyanate (B-2)] 2.2 parts are twin-screw extruders (manufactured by Toshiba Machine Co., Ltd., TEM35B, 37 mmφ, L / D = 4
Using 1), the mixture was melt-kneaded at a cylinder temperature of 190 ° C. for 5 minutes. The obtained composite resin is heated to a cylinder temperature of 200.
Injection molding at a mold temperature of 50 ° C. to prepare a test piece of the molded product of the present invention (shear at this time was 10 ³ sec ⁻¹ ),
Table 1 shows the surface specific resistance and resin property evaluation results of this test piece.

Example 2 Example 1 except that 3 parts of maleic anhydride-modified polypropylene [bound maleic acid content 5%, number average molecular weight 5,000, abbreviated as PP-MA hereinafter; corresponding to dispersant (C)] was added.
The same materials and conditions were used for melt kneading. The obtained composite resin was injection molded under the same conditions by using the same injection molding machine as in Example 1 to prepare a molded body test piece. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 1.

Example 3 89 parts of PEG2000 and 11 parts of MDI were used in Example 1.
Polyurethane (hereinafter abbreviated as PU-1) was obtained by melt-kneading for 5 minutes at a cylinder temperature of 190 ° C. using the same twin-screw extruder. 80 parts PP, 20 parts PU-1 and P
3 parts of P-MA was melt-kneaded using the same twin-screw extruder as in Example 1 under the same conditions. The obtained composite resin was used in Example 1
Using the same injection molding machine as above, injection molding was performed under the same conditions to prepare a molded body test piece. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 1.

Comparative Example 1 PP 99 parts, polyhydric alcohol fatty acid ester type antistatic agent (Chemist 1100 manufactured by Sanyo Kasei Co., Ltd.) 1
Parts were melt-kneaded using the same twin-screw extruder as in Example 1. The obtained composition was injection molded under the same conditions by using the same injection molding machine as in Example 1 to prepare a test piece. The characteristics of this test piece were evaluated in the same manner as in Example 1. The results of the characteristic evaluation are shown in Table 1.

[0043]

[Table 1]

Example 4 Polystyrene (Asahi Kasei Polystyrene 60 manufactured by Asahi Kasei Corporation)
0, hereinafter abbreviated as PS) 80 parts, PEG2000 17.
8 parts, MDI 2.2 parts and one end hydroxypolystyrene (Mw = 3300; dispersant) 3 parts were added to a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd. TEM35B, 37 mmφ, L / D = 4).
Using 1), the mixture was melt-kneaded at a cylinder temperature of 200 ° C. for 5 minutes. The obtained composite resin is heated to a cylinder temperature of 200.
Injection molding at a mold temperature of 50 ° C. and a mold temperature of 50 ° C. to prepare a test piece of the molded article of the present invention, and the surface resistivity of this test piece was evaluated. The results of the characteristic evaluation are shown in Table 2.

Comparative Example 2 99 parts of PS and 1 part of a polyhydric alcohol fatty acid ester type antistatic agent (Chemistat 1100 manufactured by Sanyo Chemical Industry Co., Ltd.) were melt-kneaded under the same conditions as in Example 4. The obtained composition was injection molded under the same conditions using the same injection molding machine as in Example 4 to prepare test pieces. The characteristics of this test piece were evaluated in the same manner as in Example 4. The results of the characteristic evaluation are shown in Table 2.

[0046]

[Table 2]

[0047]

EFFECTS OF THE INVENTION The molded article of the present invention has a permanent antistatic property which cannot be achieved by the conventional techniques and has excellent resin properties. The permanent antistatic method using the polyurethane (B) according to the present invention has a molding processability such that the molding temperature can be extended to a lower temperature range as compared with the conventionally known methods using a permanent antistatic polymer. Are better. Also, the appearance of the molded product is excellent. Because of the above effects, the molded product of the present invention is useful as a molding material for various applications requiring antistatic properties such as containers, cases, automobile parts, hoses, films, and various housing materials.

Claims (11)

[Claims] 1. A composite of a thermoplastic resin (A) and a polyurethane (B) having a polyoxyethylene chain,
(B) A permanent antistatic composite resin molded product in which at least a part of the phase is dispersed like streaks in the composite resin surface layer portion. 2. (B) is a polyfunctional compound containing active hydrogen (B
-1) and / or polyisocyanate (B-2) is a polymerization product of (B-1) and (B-2) obtained by using a compound having a polyoxyethylene chain as at least a part thereof. The molded article described. 3. The molded product according to claim 1, wherein (A) is 60 to 95% by weight, and the total amount of polyoxyethylene chains contained in (B) is 5 to 40% by weight. 4. The molecular weight of (B) is from 6,000 to 20.
The molded article according to claim 1, 2 or 3 having a weight average molecular weight of 10,000. 5. The polyoxyethylene chain contained in (B) is 4 to 70 oxyethylene chains.
The molded product according to any one of to 4. 6. The molded product according to claim 1, wherein (A) is a polyolefin-based thermoplastic resin. 7. The molded product according to claim 6, comprising a composite of (A), (B) and the following dispersant (C). Dispersant (C): a modified polyolefin dispersant having active hydrogen, a (anhydrous) carboxylic acid group, or a carboxylic acid halide group, or a polyolefin-polyurethane copolymer dispersant. 8. The molded product according to claim 1, wherein (A) is a styrene-based thermoplastic resin. 9. (A), (B) and the following dispersant (C)
The molded article according to claim 8, which is formed of a composite body of Dispersant (C): Styrene-based dispersant having active hydrogen, (anhydrous) carboxylic acid group, or carboxylic acid halide group, or [styrene-based (co) polymer] -polyurethane copolymer-based dispersant. 10. (A) is aromatic polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyacetal, polyphenylene oxide, polyether ether ketone, polyphenylene sulfide,
The molded product according to any one of claims 1 to 5, which is a thermoplastic resin selected from the group consisting of and polysulfone. 11. In the molten (A), (B-1) and (B)
-2) polymerized complex, or (A) and (B)
Add at least 10 ² sec ^-1 to the composite obtained by melting and kneading
The permanent antistatic method for a molded article according to any one of claims 1 to 10, wherein at least a part of the phase (B) is dispersed in a streak form in the surface layer of the composite resin by applying the shearing.