JPH0987461A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition permanently having excellent antistaticity, excellent in moldability and mechanical properties such as flexural elastic modulus, and useful in the fields of electric and electronic equipmentds by compounding an aromatic polycarbonate resin with a specific vinylic polymer. SOLUTION: This resin composition comprises (A) 99-50wt.% of an aromatic polycarbonate resin (preferably resin having a viscosity-average mol.wt. of 14000-50000), and (B) 1-50wt.% of a vinylic polymer comprising (i) 2-100mol.% of repeating units derived from a styrenesulfonic acid phosphonium salt of the formula (R<1> -R<4> are each a 1-18C aliphatic or aromatic hydrocarbon, an aralkyl, an alkylaryl; X<1> , X<2> are each H, Cl, Br; Y<1> -Y<4> are each H, Cl, Br, a 1-6C hydrocarbon) and (ii) 98-0mol.% of repeating units derived from a vinylic monomer (preferably having H and Cl) except the above salt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having a permanent antistatic property and excellent mechanical strength and moldability.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent mechanical properties and are widely used in various fields such as electric and electronic equipment fields, automobile fields, machine fields, medical fields and the like. However, the polycarbonate resin has a high electric resistivity,
Since it is easily charged, it may cause various problems due to static electricity. For example, when a resin molded product is electrostatically charged, it has the drawbacks that dust or dirt may adhere to the surface to impair its appearance and reduce the product value, or it may cause an electric shock phenomenon and hinder its handling. There is. In addition, in the electric / electronic parts, it may cause an erroneous operation and may cause a serious problem in function. Therefore, it has been desired to develop a material having a so-called permanent antistatic property, which is capable of imparting an antistatic function and retaining its performance permanently.

Conventionally, in order to impart antistatic properties to polymer materials, a method of applying an antistatic agent on the surface, a method of kneading various low molecular weight antistatic agents into a resin, and the like are generally performed. There is. For example, an example of using a phosphonium salt as a low molecular weight antistatic agent for the purpose of imparting antistatic properties to a polycarbonate resin is disclosed.
No. 14267, a method of kneading a phosphonium sulfonate and a phosphite is disclosed in JP-A-2-28495.
JP-A-5-171024 discloses a method of kneading a phosphonium sulfonate and a boric acid derivative, and JP-A-5-171024 discloses a method of kneading a phosphonium sulfonate and a sulfur atom-containing ester compound. Japanese Patent No. 62215 discloses a method of kneading a phosphonium sulfonate, a sulfur atom-containing ester compound, and hydrotalcites.

However, any of the methods has only realized a temporary antistatic property, and the antistatic property disappears after washing with water or the surface is wiped off, and the antistatic property changes with time. There were problems such as performance changes. Further, depending on the conditions, there is a problem that the kneading component bleeds out on the surface and the quality as a raw material deteriorates. Such problems are common when using a low molecular weight antistatic agent, and continuous impartation of antistatic properties has been desired.

[0005]

The object of the present invention is to provide a polycarbonate resin composition having a permanent antistatic property and excellent in mechanical properties, thermal stability and moldability, and to provide a permanent antistatic property. Another object of the present invention is to provide a polycarbonate resin composition having excellent mechanical properties, thermal stability, moldability and transparency.

[0006]

The present invention has been made to solve the above-mentioned problems, and its gist is represented by 99 to 50% by weight of an aromatic polycarbonate resin and the following general formula (1). 1 to 50% by weight of a vinyl polymer comprising 2 to 100 mol% of repeating units derived from phosphonium styrenesulfonate and 98 to 0 mol% of repeating units derived from vinyl monomers other than phosphonium styrenesulfonate salt % In the polycarbonate resin composition.

[0007]

Embedded image

(In the formula 1, R ^{1 to} R ⁴ are respectively
An aliphatic hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group, an aralkyl group, or an alkylallyl group, X ¹
To X ² are each hydrogen, chlorine or bromine, and Y ¹ to
Y ⁴ is hydrogen, chlorine, bromine, or has 1 carbon atom, respectively.
~ 6 hydrocarbons. )

Hereinafter, the present invention will be described in detail. The aromatic polycarbonate resin in the present invention is a polymer obtained by a phosgene method of reacting various dihydroxydiaryl compounds with phosgene, or a transesterification method of reacting a dihydroxydiaryl compound with a carbonic acid ester such as diphenyl carbonate, or a copolymer. A typical example of the union is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxydiaryl compounds include bisphenol A, bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, and 2,2 '-(4-hydroxyphenyl).
Butane, 2,2 '-(4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2'-bis (4-hydroxy-3-methylphenyl) propane, 1,1'-bis ( 4-hydroxy-3
-Tert-butylphenyl) propane, 2,2'-bis (4
-Hydroxy-3-bromophenyl) propane, 2,
2'-bis (4-hydroxy-3,5 dibromophenyl) propane, 2,2'-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5 dichlorophenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclopentane, 1,1′-bis (4-
Bis (hydroxyaryl) cycloalkanes such as hydroxyphenyl) cyclohexane, 4,4′-
Dihydroxy diphenyl ethers, dihydroxy diaryl ethers such as 4,4'dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-
Dihydroxydiaryl sulfides such as 3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4, Examples thereof include dihydroxydiarylsulfones such as 4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

These may be used alone or in admixture of two or more, but in addition to these, piperazine, dipiperidyl, hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like may be mixed and used. The viscosity average molecular weight of the aromatic polycarbonate is preferably 14,000 to 50,000, more preferably 15,000 to 40,0, from the viewpoint of balance between fluidity and strength.
00.

The vinyl polymer in the present invention includes:
2-100 mol% of repeating units derived from phosphonium styrenesulfonate represented by the general formula (1)
And a vinyl polymer comprising 98 to 0 mol% of repeating units derived from vinyl monomers other than styrene phosphonium sulfonate. The styrene sulfonic acid phosphonium salt is represented by the following general formula (2) and is composed of a styrene sulfonate anion and an organic phosphonium cation.

[0013]

Embedded image

In the formula 2, R ^{1 to} R ⁴ are each an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group,
It is an aralkyl group or an alkylallyl group. X ^{1 to} X ²
Are respectively hydrogen, chlorine or bromine. Y ^{1 to} Y
⁴ is hydrogen, chlorine, bromine, or 1 to 4 carbon atoms, respectively.
6 hydrocarbons. Examples of the styrene sulfonate anion include styrene sulfonate, α-chlorostyrene sulfonate in which the α-position and β-position hydrogen of styrene sulfonate are replaced by chlorine or bromine, β-chlorostyrene sulfonate, α-bromostyrene sulfonate, β-bromostyrene. Examples thereof include anions such as sulfonate. Further, a sulfonate anion in which hydrogen of an aromatic ring constituting styrene is replaced by chlorine, bromine, or a hydrocarbon having 1 to 6 carbon atoms can be given.

As the organic phosphonium cation, 1)
Tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, trioctylmethylphosphonium, tributylethylphosphonium, trimethylbutylphosphonium, triethyloctylphosphonium, tributyloctylphosphonium, trimethyllaurylphosphonium, trimethylstearylphosphonium, etc., Phosphonium having an aliphatic hydrocarbon group having 1 to 18 carbon atoms, 2) Phosphonium having an aromatic hydrocarbon group such as tetraphenylphosphonium, triphenylethylphosphonium, and triphenylmethylphosphonium, 3) Triphenylbenzylphosphonium , Tritoluylbutylphosphonium, tributylbenzylphosphonium, etc. Le Motomata are phosphonium having an alkyl aryl group. Of these, tetrabutylboronium and tetraphenylphosphonium are preferable.

The phosphonium styrenesulfonate in the present invention is constituted by any combination of the above-mentioned styrene sulfonate anion and organic phosphonium cation. The styrene phosphonate phosphonium salt represented by the general formula (2) may be produced by mixing a corresponding metal salt or ammonium salt of styrene sulfonate and a quaternary phosphonium salt in a solvent to produce an inorganic salt as a by-product. Examples of the method include washing with water and separating, or extracting the target monomer with an organic solvent such as methanol, isopropanol, and acetone. More specifically, for example, in the case of tetrabutylphosphonium styrenesulfonate, 20.6 parts by weight of sodium styrenesulfonate, 33.9 parts by weight of tetrabutylphosphonium bromide, and 200 parts by weight of water are charged into a flask and heated to 80 ° C. After stirring for 1 hour at room temperature, the target monomer that separates as an oil layer is separated, washed with 50 parts by weight of warm water, and dehydrated with an evaporator, whereby the yield can be about 90%.

The vinyl monomer other than the phosphonium styrenesulfonate salt used in the present invention is a vinyl monomer copolymerizable with the phosphonium styrenesulfonate salt, and examples thereof include aromatic vinyls. Specifically, styrene, methylstyrene, and α-position of styrene,
At least one of the hydrogen atoms of the aromatic ring constituting these styrenes is chlorine, and α-chlorostyrene in which hydrogen at the β-position is replaced by chlorine or bromine, β-chlorostyrene, α-bromostyrene, β-bromostyrene. , Bromine, or C1-6 hydrocarbon substituted monomers.

Further, vinyl ethers such as methyl vinyl ether and methoxy vinyl ether, vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate, acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate. Examples thereof include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, allyl esters such as allyl acetate and allyl caprylate, maleic anhydride, itaconic acid or ester derivatives thereof, acrylamide, methacrylamide, and acrylonitrile. Two or more kinds of vinyl monomers other than the styrene phosphonium phosphonium salt to be combined with the styrene phosphonium phosphonium salt may be used.

The type of the vinyl monomer copolymerized with the phosphonium styrenesulfonate salt may be appropriately determined in consideration of the balance between the antistatic property and other physical properties. Typical vinyl monomers include, for example, styrene. When an aromatic vinyl compound is used, a vinyl polymer having good heat resistance is obtained, and when maleic anhydride is used, a vinyl polymer excellent in compatibility is obtained.

Further, in order to obtain a polycarbonate resin composition having excellent transparency, it is preferable to blend a vinyl polymer having chlorine and / or bromine in the repeating unit. Alternatively, it is a polymer containing a repeating unit derived from a phosphonium styrenesulfonate having bromine and / or a repeating unit derived from a vinyl monomer having chlorine or bromine. To obtain a vinyl polymer having chlorine and / or bromine in the repeating unit, the styrene sulfonate anion constituting the phosphonium styrenesulfonate is substituted with chlorine and bromine at the α-position and β-position hydrogen of the styrene sulfonate. Anions such as α-chlorostyrene sulfonate, β-chlorostyrene sulfonate, α-bromostyrene sulfonate and β-bromostyrene sulfonate, and a sulfonate in which at least one hydrogen atom of the aromatic ring constituting styrene is replaced with chlorine or bromine. It is preferable to use an anion, and as vinyl monomers other than styrene phosphonium sulfonate, α-position of styrene, β
At least one of the hydrogen atoms in the aromatic ring constituting α-chlorostyrene, β-chlorostyrene, α-bromostyrene, β-bromostyrene, styrene in which the hydrogen at the position is replaced with chlorine or bromine is replaced with chlorine or bromine. It is preferable to use the above monomers.

The content of the repeating unit derived from the phosphonium styrenesulfonate salt in the vinyl polymer containing the repeating unit derived from the phosphonium styrenesulfonate salt represented by the general formula (1) is 2 to 100 mol. %. If it is less than 2 mol%, the antistatic property is difficult to be exhibited when the vinyl polymer is kneaded into the polycarbonate resin. From the viewpoint of the balance between antistatic property, heat resistance and mechanical properties, it is preferably 20 to 100 mol%.

The structure of the vinyl polymer in the present invention as a polymer may be random, block, graft or the like depending on the polymerization method. The above-mentioned polymerization method is a bulk in which the monomer represented by the general formula (2) is directly dissolved in another vinyl-polymerizable monomer or a low-polymerization product thereof to perform copolymerization in the presence of a polymerization initiator. polymerization,
Solution polymerization using an organic solvent, emulsion polymerization or suspension polymerization using water as a solvent or dispersion medium, and the like can be applied. It is also possible to graft-polymerize the monomer represented by the general formula (2) into any vinyl polymer in the chain or at the terminal of the vinyl polymer. The present invention is also not particularly limited in terms of the polymerization mode, and radical polymerization, ionic polymerization, living polymerization, etc. can be arbitrarily adopted.

The weight average molecular weight of the vinyl polymer in the present invention is preferably 5,000 to 200,000. If it is less than 5,000, the mechanical strength tends to decrease, and if it exceeds 200,000, the antistatic property and processability tend to deteriorate. From the viewpoint of the balance of mechanical strength, antistatic property and workability, more preferably 10,000 to 100,
000.

The polycarbonate resin composition of the present invention comprises
The aromatic polycarbonate resin comprises 99 to 50% by weight and the vinyl polymer 1 to 50% by weight. When the amount of the vinyl polymer is less than 1% by weight, the antistatic property is insufficiently expressed, and when it is more than 50% by weight, heat resistance and mechanical properties are deteriorated. The blending amount of the vinyl polymer is preferably 5 to 30% by weight from the viewpoint of the balance among antistatic property, heat resistance and mechanical properties.

In order to further improve the antistatic property, the polycarbonate resin composition of the present invention contains an antistatic agent such as a metal salt of alkylsulfonic acid or an anionic, cationic or nonionic surfactant. It can also be added.

The polycarbonate resin composition of the present invention is
Further, if necessary, in order to improve the performance as a molding resin, various well-known additives such as glass fiber, glass flake, glass beads, carbon fiber, and mineral fiber within the range of not impairing the properties of the composition. , Reinforcing agents such as metal fibers and ceramic whiskers, fillers such as titanium oxide, silica, alumina, carbon black and calcium carbonate,
Mold release agents such as paraffin wax, polyethylene wax, beeswax, and silicone oil, various plasticizers, and antioxidants such as hindered phenol type, phosphorous acid ester type, sulfur-containing ester compound type, halogen compounds, phosphoric acid compounds, etc. Flame retardants, UV absorbers or weather resistance imparting agents, dyes, pigments, foaming agents and the like, and as resin components, polyester resins such as PET and PBT, polyphenylene ether, nylon 6 and nylon 66. , Nylon 12, Nylon MXD6, etc. Nylon, various nylon elastomers, polystyrene, ABS, AS, M
Styrene-based resins such as S, various acrylic resins, olefin-based resins such as polyethylene, polypropylene, and ethylene-propylene copolymers, and isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic-based elastomer components. Elastomer, ionomer resin, phenoxy resin, polycaprolactam, etc. can be contained.

The polycarbonate resin composition of the present invention is
Aromatic polycarbonate, a vinyl-based copolymer containing the phosphonium styrenesulfonate represented by the general formula (1), and various additive components, resin components, elastomer components, and the like, which are used as necessary, are mixed and kneaded. Can be obtained by Formulation is a commonly used method,
For example, a ribbon blender, a Hensell mixer, a drum blender or the like is used. For melt kneading, various extruders,
Brabender plastograph, lab plastomill, kneader, Banbury mixer, etc. are used. The heating temperature for melt-kneading is usually selected in the range of 220 to 300 ° C. In order to prevent decomposition during kneading, the above-mentioned antioxidants are usually used in many cases.

The polycarbonate resin composition of the present invention is
Various known molding methods, such as injection molding, blow molding,
By extrusion molding, compression molding, calender molding, rotational molding and the like, molded products in the fields of electric and electronic devices, automobiles, machines, medical fields and the like can be obtained. In molding to obtain the final molded product, it is preferable to control the resin temperature to 220 to 300 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

EXAMPLES "Parts" in the examples means "parts by weight". still,
The resin compositions of Examples and Comparative Examples were molded into molded pieces by injection molding, and then the performance was evaluated by the following test methods.

1) Antistatic property The antistatic property was evaluated by measuring the surface specific resistance value. Using an Ultra High Resistance Meter (Advantest), according to ASTM D-257,
A test piece (a disk with a diameter of 10 cm and a thickness of 3 mm) is heated at a temperature of 2
After standing for 3 days or more at 3 ° C and 50% humidity,
The surface specific resistance value was measured. The smaller the value, the better the antistatic property can be evaluated.

2) Permanent antistatic property The test piece evaluated for antistatic property as described above was washed with water and then left standing for 3 days or longer under the conditions of a temperature of 23 ° C. and a humidity of 50%.
After adjusting the condition, the surface resistivity of the water-washed product was measured. It can be said that the material is excellent in permanent antistatic property if the surface resistivity without washing treatment is low and the surface resistivity of the rinsed product is kept low. In addition, the washing process is 8m inside diameter
While flowing tap water at a flow rate of 5 L / min from the hose of m, on a molded test piece placed 15 cm directly under the hose,
The tap water was moved at a vertical angle for 40 seconds so as to be uniformly applied. After that, demineralized water was sprinkled on the test piece, and it was simply replaced and washed.

3) Mechanical Properties The flexural modulus was measured by ASTM D790.
The monomers used to produce the vinyl-based monomer are as follows. Vinyl monomer A; styrene sulfonic acid tetrabutylphosphonium salt Vinyl monomer B; styrene sulfonic acid tetraphenylphosphonium salt Vinyl monomer C; 3-bromostyrene sulfonic acid tetrabutylphosphonium salt Vinyl monomer D; Styrene vinyl Monomer E; p-bromostyrene vinyl monomer F; methyl methacrylate vinyl monomer G; maleic anhydride The antistatic agent used in Comparative Examples is as follows. Antistatic agents H; dodecylbenzenesulfonic acid tetrabutylphosphonium salt antistatic agent I; R-SO ₃ Na, Nikko Petrochemical Industry Co., atrai AS-1030

Examples 1 to 8 Monomers (total 3 mol) having the monomer composition shown in Table 1 and 3000 g of toluene as a solvent were charged into a polymerization reactor and uniformly mixed. Then add 3 g of α, α'-azobisisobutyronitrile,
The reaction was continued in a nitrogen atmosphere at 100 ° C. for 24 hours to complete the polymerization. The reaction solution was cooled to room temperature and then poured into methanol with vigorous stirring to precipitate a polymer. After the precipitate was washed and filtered off, it was dried under vacuum. The sulfur content in the obtained vinyl copolymer was quantitatively analyzed with an elemental analyzer, and from this result, the copolymerization mol% of the styrene phosphonate phosphonium salt monomer was copolymerized.
Was calculated.

Each of the obtained vinyl copolymers, polycarbonate resins (manufactured by Mitsubishi Engineering Plastics Co., Ltd., Iupilon S-3000, viscosity average molecular weight 21,000), and Asahi Denka Co., Ltd. as heat stabilizers The amount of Adekastab PEP-36 under the trade name of No. 3 shown in Table 1 was weighed and blended with a tumbler for 10 minutes. Then, the blended product was melt-kneaded at a cylinder temperature of 270 ° C. using a twin-screw extruder, and pelletized.

The obtained pellets were dried and injection-molded at 270 ° C. to obtain test pieces for evaluating physical properties. The surface specific resistance value (unit Ω / CM ² ) after humidity control and the surface specific resistance value of the water-washed product were measured to evaluate the permanent antistatic property. The flexural modulus (unit: Kgf / CM ² ) was measured as the mechanical property. The measurement results are shown in Table-1.

Comparative Example 1 Pelletization was performed in the same manner as in Example 1 except that the vinyl polymer was not blended, and the obtained pellets were evaluated in the same manner as in Example 1. . The results are shown in Table 1.

[Comparative Examples 2 to 3] Pelletization was carried out in the same manner as in Example 1 except that the vinyl polymer was not blended but the antistatic agent shown in Table 1 was blended. The obtained pellets were evaluated in exactly the same manner as in Example 1. The results are shown in Table 1.

[0038]

[Table 1]

[0039]

The polycarbonate resin composition of the present invention has excellent permanent antistatic properties, mechanical properties such as flexural modulus, and moldability. Further, in the polycarbonate resin composition of the present invention, a resin composition containing a vinyl polymer having chlorine or bromine has a permanent antistatic property, and has mechanical properties, thermal stability, moldability and transparency. It has excellent properties. Molded articles obtained from the polycarbonate resin composition of the present invention have dust or dirt attached to the surface due to electrostatic charge to impair the appearance and reduce the commercial value, or cause erroneous operation to cause a serious problem in function, or an electric shock phenomenon. Since it does not cause charging troubles such as the occurrence of troubles in its handling, it has high utility value in many fields such as electric and electronic equipment fields, automobile fields, machine fields, medical fields, and the like.

Claims (4)

[Claims] 1. An aromatic polycarbonate resin 99 to 50.
2 to 1 of repeating units derived from styrene sulfonic acid phosphonium salt represented by the following general formula (1)
A polycarbonate resin composition containing 100 mol% of a vinyl polymer, which is composed of 98 to 0 mol% of repeating units derived from a vinyl monomer other than phosphonium styrenesulfonate, and 0 to 50 mol%. Embedded image (In the formula 1, each of R ^{1 to} R ⁴ has 1 to 1 carbon atoms.
8 is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, or an alkylallyl group, X ^{1 to} X ² are each hydrogen, chlorine or bromine, and Y ^{1 to} Y ⁴ are each It is hydrogen, chlorine, bromine, or a hydrocarbon having 1 to 6 carbon atoms. ) 2. The polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin having a viscosity average molecular weight of 14,000 to 50,000. 3. A repeating unit derived from the phosphonium styrenesulfonate represented by the general formula (1), wherein at least one of X ¹ , X ² , and Y ^{1 to} Y ⁴ is chlorine or bromine. The polycarbonate resin composition according to claim 1 or 2. 4. The repeating unit derived from a vinyl monomer other than phosphonium styrenesulfonate is a repeating unit derived from a vinyl monomer having chlorine or bromine. The polycarbonate resin composition according to any one of 3 above.