JPH09194710A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition useful as electric/ electronic parts, etc., hardly causing reduction in antistatic properties, excellent in mechanical properties, thermal stability and moldability, by blending an aromatic polycarbonate resin with a polyamide resin and an organic sulfonate type antistatic agent. SOLUTION: This polycarbonate resin composition is obtained by blending (A) 100 pts.wt. of an aromatic polycarbonate resin with (B) 1-60 pts.wt., preferably 5-50 pts.wt. of a polyamide resin and (C) 0.1-20 pts.wt., preferably 0.5-5 pts.wt. of an organic sulfonate type antistatic agent of the formula R-SO3 M (R is a 1-32C aliphatic hydrocarbon or aromatic hydrocarbon group; M is an alkali metal) in a melt state. The composition does not require a polymer type antistatic agent and is applicable in the field of automobiles, machines and medical practice.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a permanent antistatic polycarbonate resin composition, and more particularly to a permanent antistatic polycarbonate resin composition excellent in 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. Further, in the electric / electronic parts, there are cases where erroneous operation is caused and serious functional problems are caused. 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 salt and a boric acid derivative, and JP-A-5-171024 discloses a method of kneading a phosphonium sulfonate salt and a sulfur atom-containing ester compound. . But,
Both methods achieve only temporary antistatic property, and the antistatic property disappears when washed with water or the surface is wiped off, and the antistatic property changes with time, resulting in performance change. There was a problem such as. 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 not only when using a phosphonium sulfonate salt as an antistatic agent but also when using other low molecular weight antistatic agents, and it is possible to impart a continuous antistatic property. Has been desired.

On the other hand, the resin has a continuous antistatic property, that is,
It is known to use polyetheresteramide as a method of imparting a permanent antistatic property. However, when a polyether ester amide is blended with a polycarbonate resin and kneaded and molded, the temperature at the time of kneading or molding is high, so that there is a problem that a molded product is colored or a defective appearance is likely to occur due to generation of silver or the like. . Also,
Since the polyether ester amide has poor compatibility with other thermoplastic resins, it is difficult to obtain a resin composition having desirable mechanical properties due to delamination or poor impact strength. was there.

Therefore, JP-A-60-23435 discloses a method of using a modified vinyl copolymer containing a carboxyl group in a polyether ester amide as a compatibilizing agent. Japanese Patent No. 70735 proposes a method in which a rubber-modified styrene thermoplastic resin containing a vinyl monomer having a hydroxyl group as a copolymerization component is used as a compatibilizer. However, although the compatibility problem has been improved by these methods, a large amount of the compatibilizing agent needs to be added, and there is a drawback that the antistatic property is likely to decrease.

[0006]

An object of the present invention is to provide a permanent antistatic polycarbonate resin composition which is excellent in mechanical properties, thermal stability and moldability and is inexpensive.

[0007]

The present invention has been made to solve the above-mentioned problems, and its gist is to make 100 parts by weight of an aromatic polycarbonate resin, 1 to 60 parts by weight of a polyamide resin and an organic sulfone. Acid salt type antistatic agent 0.
1 to 20 parts by weight of a permanent antistatic polycarbonate resin composition.

Hereinafter, the present invention will be described in detail. As the aromatic polycarbonate resin in the present invention, 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 polymer is 2,2-bis (4
-Hydroxyphenyl) propane (bisphenol A)
The polycarbonate resin produced from Examples of the dihydroxydiaryl compound include bis (4-hydroxyphenyl) methane in addition to bisphenol A,
1,1'-bis (4-hydroxyphenyl) ethane,
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,
Bis (hydroxyaryl) alkanes such as 2,2′-bis (4-hydroxy-3,5dichlorophenyl) propane, 1,1′-bis (4-hydroxyphenyl)
Bis (hydroxyaryl) cycloalkanes such as cyclopentane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′dihydroxy-3,3′-dimethyldiphenyl ether Dihydroxy diaryl ethers such as 4,4'-dihydroxy diphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy diphenyl sulfoxide, 4, , 4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, dihydroxydiaryl sulfoxides, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, and the like. Examples thereof include hydroxydiaryl sulfones.

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 40,000, from the viewpoint of balance between fluidity and strength. Here, the viscosity average molecular weight is calculated from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.

The polyamide resin in the present invention includes:
It is a polyamide containing amino acids, lactams, or diamines and dicarboxylic acids as main constituent components. Specific examples of the constituents include lactams such as ε-caprolactam, enantolactam and ω-laurolactam, amino acids such as ε-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, tetramethylenediamine, hexamethylenediamine. , Undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine , 1,3-
Bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-D-aminocyclohexylpropane,
Diamines such as isophoronediamine, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanenic acid, 1,
There are dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and dimer acid. These constituents are subjected to the polymerization in the form of a single kind or a mixture of two or more kinds, and any of the obtained polyamide homopolymers or copolymers can be used in the present invention. The polyamide resin in the present invention is preferably an aliphatic polyamide resin, and specific examples of the aliphatic polyamide resin include polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 6).
6), polyhexamethylene sebacamide (nylon 61
0), polyundecane amide (nylon 11), polydecane amide (nylon 12), copolymers and mixtures of these polyamides, and the like. Among them, polyamides suitable for the present invention are nylon 6 and nylon 66.

The method for producing the polyamide resin in the present invention is not particularly limited, and a polyamide produced by ordinary melt polymerization can be used. The degree of polymerization is also not particularly limited, and the relative viscosity of 96% concentrated sulfuric acid at 25 ° C is 1.5.
Any material in the range of to 7.0 can be used. There is also no particular limitation on the balance of the terminal groups, and the amount of amino terminal groups and the amount of carboxyl terminal groups,
Either a substantially balanced polyamide or a polyamide adjusted so that one of them is more than the other can be used, but in order to obtain a more stable composition,
Polyamides having less amino end groups than carboxyl end groups are preferred.

The blending amount of the polyamide resin is 1 to 60 parts by weight with respect to 100 parts by weight of the polycarbonate resin. When the compounding amount is less than 1 part by weight, the antistatic property is not sufficiently exerted, and when the compounding amount exceeds 60 parts by weight, the mechanical properties and heat resistance of the polycarbonate resin composition are likely to be deteriorated and the dimensional stability due to moisture absorption is reduced. Also tends to fall. The blending amount of the polyamide resin is 100 parts by weight of the polycarbonate resin,
Preferably it is 5 to 50 parts by weight.

When melt-kneading the polycarbonate resin and the nylon resin, the polycarbonate resin is decomposed,
The molecular weight of the polycarbonate resin may decrease significantly,
Physical properties such as strength deteriorate. In order to prevent this, it is also preferable to mix a polyamide resin having a water content of 0.05 to 3.0% by weight and melt-knead the polyamide resin. When the water content is less than 0.05% by weight, deterioration of the polycarbonate resin is likely to occur due to the interaction with the polyamide resin during melt-kneading, and when it exceeds 3.0% by weight,
Problems such as foaming during melting and kneading and a decrease in the molecular weight of the polycarbonate resin are likely to occur. The water content of the polyamide resin is preferably 0.1 to 2.5% by weight. The polycarbonate resin may be dried or may have a saturated water absorption amount at normal room temperature. When a nylon resin having a water content of less than 0.05% by weight is used, water corresponding to the water content may be present during melt kneading.

The organic sulfonate type antistatic agent in the present invention is a compound represented by the general formula (1). R-SO ₃ M (1) formula (1), R is a linear or branched aliphatic hydrocarbon group or an aromatic hydrocarbon group of 1 to 32 carbon atoms, preferably from 8 to 28 carbon atoms , A straight-chain or branched aliphatic hydrocarbon group or aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group, and may have a substituent such as an alkyl group. M is
Examples thereof include alkali metal, alkaline earth metal, phosphonium ion, ammonium ion and carbonium ion. M is preferably an alkali metal, and most preferably sodium ion.

Specific examples of the organic sulfonate-type antistatic agent represented by the general formula (1) include sodium n-hexylsulfonate, sodium n-dodecylsulfonate, and n.
-Alkyl sulfonate type antistatic agents such as sodium octadecyl sulfonate and potassium dodecyl sulfonate,
Alkylbenzene sulfonic acid metal salt type antistatic agents such as sodium decylbenzene sulfonate, sodium dodecylbenzene sulfonate, sodium stearyl benzene sulfonate, sodium octyl benzene sulfonate, potassium dodecyl benzene sulfonate, sodium octyl naphthalene sulfonate, dodecyl naphthalene sulfone Examples thereof include alkyl naphthalene sulfonic acid metal salt type antistatic agents such as sodium acid salt and potassium dodecyl naphthalene sulfonate. Organic sulfonate type antistatic agents are
You may use 1 type or in mixture of 2 or more types.

The compounding amount of the organic sulfonate type antistatic agent is 100 parts by weight of the polycarbonate resin composition.
0.1 to 20 parts by weight. If the blending amount exceeds 20 parts by weight, the mechanical properties of the polyester resin composition are likely to be significantly reduced, and if it is less than 0.1 parts by weight, the permanent antistatic property tends to be insufficient. The blending amount of the organic sulfonate type antistatic agent is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight from the viewpoint of the balance between antistatic properties and mechanical properties. .

In order to further improve the antistatic property, the polycarbonate resin composition of the present invention is used in combination with the above organic sulfonate type antistatic agent, in combination with other anionic surfactants, cationic or non-ionic surfactants. It is also possible to add an antistatic agent such as an ionic surfactant.

The polycarbonate resin composition of the present invention is
Further, if necessary, in order to improve the performance as a molding resin, within a range that does not impair the characteristics of the composition, various known additives such as glass fiber, glass flakes, glass beads, carbon fiber, mineral fiber, Metal fibers, reinforcing agents for ceramics whiskers, titanium oxide, silica, alumina,
Carbon black, calcium carbonate and other fillers, paraffin wax, polyethylene wax, bees wax, mold release agents such as silicone oil, various plasticizers, hindered phenols, phosphite sester, sulfur-containing ester compounds, etc. Agents, halogen compounds, flame retardants such as phosphoric acid compounds, ultraviolet absorbers or weather resistance agents, dyes, pigments,
A foaming agent or the like may be contained, and as the resin component, P
Polyester resin such as ET and PBT, styrene resin such as polyphenylene ether, polystyrene, ABS, AS and MS, olefin resin such as various acrylic resins, polyethylene, polypropylene, ethylene-propylene copolymer, and elastomer, Styrene-based,
Various elastomers such as polyester type, polyamide type, acrylic type, olefin type, ionomer resin, phenoxy resin, polycaprolactam, polyalkylene glycol and the like can be contained.

The polycarbonate resin composition of the present invention comprises
It can be obtained by mixing and kneading an aromatic polycarbonate resin, a polyamide resin, an organic sulfonate type antistatic agent, and various additive components, resin components, elastomer components and the like which are used as necessary. The compounding is carried out by a commonly used method, for example, a ribbon blender, a Henschel mixer, a drum blender or the like. Various extruders, Brabender Plastograph, Labo Plastomill, kneader, Banbury mixer, etc. are used for melt-kneading. The heating temperature for melt kneading is usually 220.
A range of ~ 300 ° C is selected. 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 comprises
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 of the present invention.

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 After the test piece evaluated for antistatic property was washed with water, it was allowed to stand for 3 days or more under the condition of temperature 23 ° C. and humidity 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, the test piece was sprinkled with demineralized water, and was easily replaced and washed. 3) Mechanical Properties The flexural modulus (kgf / cm ² ) was measured by ASTM D790. Tensile elongation (%) was measured by ASTM D638. 4) Thermal properties Deflection temperature under load (HDT, ° C) is ASTM D648
According to the above, a square columnar test piece having a cross section of 6.4 mm × 12.7 mm was measured with a high load of 18.6 kgf / cm 2. The higher this value, the better the heat resistance. 5) Water content According to JIS K6810, it was measured by the Karl Fischer method.

The details of the raw materials used in Examples and Comparative Examples are as follows. a) Polycarbonate resin (sometimes abbreviated as PC resin), Iupilon S-3000 (manufactured by Mitsubishi Engineering Plastics Co., Ltd.), viscosity average molecular weight 21,
000. b) Polyamide resin, nylon 6, Novamid 1010
(Mitsubishi Engineering Plastics Co., Ltd.) c) Polyamide resin, nylon 66, Novamid 301
0 (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) d) Polyamide resin, nylon 610, Amylan CM2
001 (manufactured by Toray Industries, Inc.) e) Antistatic agent, sodium alkyl sulfonate, Atrai AS-1030 (Nikko Petrochemical Industry Co., Ltd.) f) Heat stabilizer (phosphite ester type), ADEKA STAB P
EP-36 (manufactured by Asahi Denka Co., Ltd.)

Examples 1 to 5 Polycarbonate resin (water content 0.2% by weight), polyamide resin (water content is shown in Table-1), antistatic agent, heat stabilizer
The amounts described in 1 were weighed and blended with a tumbler for 10 minutes, and 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. Bending elastic modulus (unit: Kgf / CM ² ) and tensile elongation (%) were measured as mechanical properties. Table 1 shows the measurement results.

Comparative Example 1 Polycarbonate resin (moisture content 0.2% by weight) and heat stabilizer were weighed in the amounts shown in Table 1, and blended, melt-kneaded and pelletized in the same manner as in Example 1. Was made. The pellets thus obtained were evaluated for permanent antistatic properties and physical properties in the same manner as in Example 1. Table 1 shows the measurement results.

[Comparative Example 2] A polycarbonate resin (water content 0.2% by weight), an antistatic agent, and a heat stabilizer were added to the table.
The amounts described in 1 were weighed and blended, melt-kneaded and pelletized in the same manner as in Example 1. The pellets thus obtained were evaluated for permanent antistatic properties and physical properties in the same manner as in Example 1. Table 1 shows the measurement results.

[Comparative Example 3] Polycarbonate resin (moisture content 0.2% by weight), polyamide resin (moisture content 1.6% by weight) and heat stabilizer were weighed in the amounts shown in Table-1, Blending, melt-kneading, and pelletization were performed in the same manner as in Example 1. The pellets thus obtained were evaluated for permanent antistatic properties and physical properties in the same manner as in Example 1. Table 1 shows the measurement results.

[0029]

[Table 1]

[0030]

EFFECTS OF THE INVENTION The permanently chargeable polycarbonate resin composition of the present invention has a permanent and excellent antistatic property and is also excellent in mechanical properties such as flexural modulus and moldability. The permanent electrostatic polycarbonate resin composition of the present invention does not use a special polymer type antistatic agent, but imparts the above properties by using a polyamide resin and a low molecular weight antistatic agent, which results in cost performance. An excellent material, a molded product obtained from this composition is a product that is deteriorated in product value by dust or dirt adhering to the surface due to electrostatic charge to impair the appearance, or causes an erroneous operation to cause a serious functional problem. It is highly useful in many fields such as electrical and electronic equipment fields, automobile fields, machine fields, medical fields, etc. because it does not cause electrification troubles such as electric shock phenomenon that hinders its handling. .

Claims (4)

[Claims] 1. A permanent antistatic polycarbonate resin composition comprising 100 parts by weight of an aromatic polycarbonate resin and 1 to 60 parts by weight of a polyamide resin and 0.1 to 20 parts by weight of an organic sulfonate type antistatic agent. Stuff. 2. The permanent antistatic polycarbonate resin composition according to claim 1, wherein the polyamide resin is an aliphatic polyamide resin. 3. The permanent antistatic property according to claim 1 or 2, wherein the organic sulfonate-type antistatic agent is an organic sulfonate-type antistatic agent represented by the general formula (1). Polycarbonate resin composition. _{R-SO 3 M (1)} ( wherein, R is a linear or branched aliphatic hydrocarbon group or an aromatic hydrocarbon group of 1 to 32 carbon atoms, M is an alkali metal, alkaline earth metal, phosphonium Ion or ammonium ion.) 4. The permanent antistatic polycarbonate resin composition according to claim 1, wherein the polyamide resin is a polyamide resin containing 0.05 to 3.0% by weight of water. Stuff.