JPH09194712A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition high in rigidity and modulus of elasticity and excellent in transparency. SOLUTION: This aromatic polycarbonate resin composition is obtained by blending 100 pts.wt. of an aromatic polycarbonate resin with 1-150 pts.wt. of glass fibers having <=0.015 difference of refractive index from that of the aromatic polycarbonate resin and 1-40 pts.wt. of a polyoxyalkylene glycol or polyoxyethylene derivative having >=50wt.% polyoxyethylene glycol component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polycarbonate resin composition, and more particularly to a transparent aromatic polycarbonate resin composition reinforced with glass fibers.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are excellent in transparency, impact resistance and heat resistance, and therefore, they are used as structural materials such as automobile parts and building materials, and optical parts such as lenses and prisms as substitute materials for glass. Has been adopted. Aromatic polycarbonate resin is lighter than glass and has the advantage of being less likely to break. On the other hand, since it has low rigidity, it has been necessary to improve it by adding an appropriate filler such as glass fiber in applications requiring high rigidity.

However, when a filler such as glass fiber or glass flake is added, the difference between the refractive index of glass and the refractive index of the aromatic polycarbonate resin is large, so that the transparency which is a major feature of the aromatic polycarbonate resin is transparency. There was a drawback that was damaged. Generally, the refractive index of resin-reinforced glass fiber is 1.555.
The refractive index of the aromatic polycarbonate resin using bisphenol A as a raw material is 1.585, and there is a large difference in refractive index between the two. The refractive index of high-refractive-index glass fibers that are currently commercially available is about 1.579, and even if an aromatic polycarbonate resin made from bisphenol A as a raw material is reinforced using this, there still remains a difference in refractive index. There was a limit to the effect of improving transparency.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polycarbonate resin composition having high rigidity, high elastic modulus and excellent transparency.

[0005]

The present invention has been made in order to solve the above problems, and the gist thereof is that 100 parts by weight of an aromatic polycarbonate resin is mixed with a refractive index of the aromatic polycarbonate resin. 1 to 150 parts by weight of glass fiber having a difference of 0.015 or less, and polyoxyalkylene glycol or polyoxyethylene derivative 1 containing 50% by weight or more of polyoxyethylene glycol component.
It exists in the aromatic polycarbonate resin composition which mix | blends-40 weight part.

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

As the dihydroxydiaryl compound,
In addition to bisphenol A, bis (4-hydroxyphenyl) methane, 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, 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 resin (value converted from solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent) is preferably 12,000 to 50,000. If the viscosity average molecular weight is less than 12,000, the strength tends to decrease, and if it exceeds 50,000, the fluidity tends to decrease. From the viewpoint of the balance between fluidity and strength, it is more preferably 15,000 to 35,000.

The glass fiber in the present invention is a glass fiber having a refractive index difference with an aromatic polycarbonate resin of 0.015 or less. Such glass fibers, the composition components of E glass used to reinforce ordinary aromatic polycarbonate resin, except for B ₂ O _3, F ₂ component, MgO, TiO _2, ZnO
It is the one in which the proportion of the components such as is increased. As a commercially available glass fiber, ECR of Asahi Fiber Glass Co., Ltd.
There is glass (refractive index 1.579).

The glass fiber is surface-treated with a surface-treating agent such as a silane coupling agent in order to increase the affinity between the resin and the glass fiber, increase the adhesiveness, and eliminate or reduce the opacity factor due to the formation of voids. Those that are preferable. Examples of the silane coupling agent include aminosilane-based, epoxysilane-based, allylsilane-based, vinylsilane-based and the like. Among these, aminosilane type is preferable.

The mixing ratio of the glass fiber is 1 to 150 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. If it is less than 1% by weight, it is insufficient to increase the rigidity of the product, and if it is 150% by weight or more, the moldability is deteriorated.
It becomes difficult to obtain a good transparent molded product. From the viewpoint of rigidity and transparency, it is preferably 5 to 100% by weight.

The polyoxyalkylene glycol containing 50% by weight or more of the polyoxyethylene glycol component in the present invention is 50 to 100% by weight of polyoxyethylene glycol component and 50 to 0% by weight of polyoxyethylene glycol other than polyoxyethylene glycol. It consists of an alkylene glycol component. Examples of the polyoxyalkylene glycol component other than polyoxyethylene glycol include polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol and the like. Polyoxyethylene glycol component 5
Specific examples of the polyoxyalkylene glycol containing 0% by weight or more include a block or random copolymer of oxyethylene and oxypropylene, a block or random copolymer of oxyethylene and tetrahydrofuran, and the like. Polyoxyethylene glycol component is 50
If it is less than wt%, the matrix resin composed of the aromatic polycarbonate resin and the polyoxyalkylene glycol becomes cloudy and the transparency is lowered.

50 parts of polyoxyethylene glycol component
The number average molecular weight (GPC measurement) of the polyoxyalkylene glycol, which is contained in an amount of at least wt%, is preferably 200 to 50,000. If the number average molecular weight is less than 200, the mechanical properties of the resulting resin composition are likely to deteriorate, and if it exceeds 50,000, the matrix resin tends to become cloudy and the transparency tends to be reduced. From the viewpoint of mechanical properties and transparency, more preferably,
It is 500 to 20,000. As the polyoxyalkylene glycol containing 50% by weight or more of the polyoxyethylene glycol component, polyoxyethylene glycol is preferable because of its excellent transparency.

As the polyoxyethylene derivative in the present invention, one or both terminals of HO (CH ₂ CH ₂ O) _n H (n = 5 to 1140), which is the structural formula of polyoxyethylene glycol, is used as an alcohol or a fatty acid. , Bisphenol A, polyoxyethylene glycol derivative obtained by reacting with phenol or nonylphenol, octylphenol, dodecylphenol and the like, sorbitan derivative of polyoxyethylene, and polyoxyethylene as a side chain of copolymer Examples thereof include graft copolymers. Specific examples of the polyoxyethylene glycol derivative obtained by reacting one end or both ends of polyoxyethylene glycol with alcohol, fatty acid, bisphenol A, and phenols include polyoxyethylene octyl ether, polyoxyethylene lauryl ether, Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene bisphenol A, polyoxyethylene bisphenol A lauric acid ester , Polyoxyethylene tetrabromobisphenol A, polyoxyethylene nonyl phenyl ether, polyoxy ether Ren octylphenyl ether, polyoxyethylene dodecyl phenyl ether, and the like.

Specific examples of the sorbitan derivative of polyoxyethylene include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and polyoxyethylene. Examples thereof include sorbitan monolaurate and polyoxyethylene sorbitan trioleate. Specific examples of the graft copolymer in which polyoxyethylene is introduced as the side chain of the copolymer include a graft in which polyoxyethylene is introduced into the side chain via maleic anhydride of styrene-maleic anhydride copolymer. Examples thereof include copolymers and styrene-maleic anhydride-allyl alcohol copolymer graft copolymers in which polyoxyethylene is introduced into the side chain via allyl alcohol.

50 polyoxyethylene glycol components
The compounding amount of the polyoxyalkylene glycol or the polyoxyethylene glycol derivative which is contained in an amount of not less than 1% by weight is 1 to 4 with respect to 100 parts by weight of the aromatic polycarbonate resin.
0 parts by weight. Since the refractive index of the matrix resin decreases as the blending amount increases, the blending amount that is equal to the refractive index of the glass fiber to be used is the optimum value for expressing transparency, but as the blending amount increases Since the heat resistance (heat distortion temperature) and the like are likely to decrease, it is desirable that the refractive index of the glass fiber used is as high as possible. From the viewpoint of transparency and heat resistance, the amount of polyoxyalkylene glycol or polyoxyethylene glycol derivative having a polyoxyethylene glycol component of 50% by weight or more is
The amount is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin.

In the present invention, when the aromatic polycarbonate resin and the polyoxyalkylene glycol or polyoxyethylene glycol derivative containing 50% by weight or more of the polyoxyethylene glycol component are mixed and kneaded, the transparency is surely ensured and the effect is obtained. In order to achieve the objective, it is preferable to have a transesterification reaction catalyst present. The reason why the addition of polyoxyalkylene glycol or polyoxyethylene glycol derivative containing 50% by weight or more of the polyoxyethylene glycol component is effective for expressing transparency is that the aromatic polycarbonate resin and the polyoxyalkylene glycol are transesterified. It is considered that this is because the refractive index of the matrix resin decreased and became close to that of glass.

Specific examples of the transesterification reaction catalyst include:
Para-toluenesulfonic acid, trifluoroacetic acid, acidic substances such as inorganic acids or Lewis acids such as boron trifluoride, basic substances such as sodium hydroxide, various amines, acetates of alkali metals or alkaline earth metals, etc. Metal salts, and compounds of zinc, manganese, cobalt, antimony, germanium, titanium, tin and the like, and preferably,
Tetraalkyl titanate, zinc acetate, stannous acetate,
Antimony trioxide and the like.

When the transesterification reaction catalyst is blended, the blending amount of the transesterification reaction catalyst is 0.001 to 0.2 with respect to 100 parts by weight of the aromatic polycarbonate resin.
It is preferably in parts by weight. If the blending amount is less than 0.001, the effect of addition is insufficient, and if it exceeds 0.2% by weight, problems such as coloring tend to occur. The amount of the transesterification reaction catalyst to be used is 10% by weight of the aromatic polycarbonate resin.
It is more preferably 0.003 to 0.1 parts by weight with respect to 0 parts by weight.

A dye may be further added to the aromatic polycarbonate resin composition of the present invention in order to obtain a molded product having an arbitrary color tone. Any dye may be used as long as it is an azo dye, a cyanine dye, a quinoline dye, a perylene dye, or the like as long as it is used in a usual thermoplastic resin. It is necessary to keep in mind that if the amount used is too large, the transparency decreases.

Further, various well-known additives can be added to the aromatic polycarbonate resin composition of the present invention within a range not impairing the present invention. As the additive, for example, a reinforcing agent such as glass flakes or glass beads having a high refractive index, a small amount of silica, alumina, a filler such as calcium carbonate, paraffin wax, polyethylene wax,
Release agents such as beeswax and silicone oil, various plasticizers, antioxidants such as hindered phenols, phosphites, sulfur-containing ester compounds and heat stabilizers, halogen compounds, flame retardants such as phosphoric acid compounds, Examples thereof include ultraviolet absorbers and weather resistance imparting agents. Further, various polymers can be blended within a range not impairing transparency. Examples of the polymer include polycaprolactone, polycaprolactone derivatives, polycyclohexanedimethylene terephthalate, P
Examples thereof include polyester resins such as ET and PBT, various nylons such as aromatic nylon and semi-aromatic nylon, polystyrene resins, polyarylate, ionomer resins and phenoxy resins.

Any method may be adopted as a method for producing the aromatic polycarbonate resin composition of the present invention. For example, as a relatively simple method, transesterification of aromatic polycarbonate resin, glass fiber, polyoxyalkylene glycol or polyoxyethylene glycol derivative containing 50% by weight or more of polyoxyethylene glycol component, and other additives as appropriate. When a catalyst is used, a method in which an ester exchange catalyst is further present and mixed by using a mixing means such as a V-type blender to prepare a batch blended product, and then melt-kneading with a vented extruder to pelletize is a method. Can be mentioned. Or as a two-step kneading method,
Aromatic polycarbonate resin, polyoxyalkylene glycol or polyoxyethylene glycol derivative containing 50% by weight or more of polyoxyethylene glycol component, and other additives are sufficiently mixed, and then melt-kneaded with an extruder with a vent. A method of producing pellets, mixing the pellets with glass fibers, and then melt-kneading them with a vented extruder can be mentioned.

Further, when an ester exchange catalyst is used, an aromatic polycarbonate resin, a polyoxyalkylene glycol or polyoxyethylene glycol derivative containing 50% by weight or more of a polyoxyethylene glycol component, and other additives are further added. Is mixed with a V-type blender or the like to prepare in advance, and the mixture is supplied from the first chute of the twin-screw extruder with a vent, and the glass fiber is supplied from the second chute in the middle of the extruder. Examples of the method include melt-kneading and pelletizing.

The heating temperature for melt kneading is usually 22.
It can be appropriately selected from the range of 0 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity, so care must be taken. Therefore, it is desirable to select the screw configuration that takes shear heat generation into consideration. The use of antioxidants and heat stabilizers is desirable in order to prevent decomposition during kneading and during molding in the subsequent process. The blending amount of the antioxidant and the heat stabilizer is 100% of the aromatic polycarbonate resin.
The amount is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, based on parts by weight.

The polycarbonate resin composition of the present invention comprises:
Various known molding methods, such as injection molding, extrusion,
By compression molding, calendar molding, rotation molding, etc.
Molded articles in the electronic device field, automobile field, machine field, construction field, medical field, etc. can be obtained. The molding method is preferably an injection molding method. The polycarbonate resin composition of the present invention is suitable as a polycarbonate resin composition for injection molding, and in injection molding for obtaining a molded product, it is preferable to control the resin temperature to 220 to 300 ° C. Even during injection molding, if the resin temperature is too high, decomposed gas is liable to be generated, which may cause opacity.

[0026]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The resin composition finally obtained or the resin composition of Comparative Example was molded into a molded piece by injection molding, and then the performance was evaluated by the following test method. 1) Mechanical Properties Bending strength and flexural modulus were measured by ASTM D790. 2) Haze, total light transmittance (Tt) A disk-shaped molded product having a thickness of 3 mm was measured using a haze meter (Suga Test Instruments Co., Ltd., trade name HGM-2DP).

Details of the raw materials used in Examples and Comparative Examples are as follows. 1) Aromatic polycarbonate resin PC, Iupilon S-3000, viscosity average molecular weight 21,
000, refractive index 1.585, manufactured by Mitsubishi Engineering Plastics Co., Ltd. 2) High refractive index glass fiber chopped strand, ECR glass; refractive index 1.57
9, average fiber diameter 16μ, manufactured by Asahi Fiber Glass Co., Ltd. 3) Glass fiber chopped strand, E glass: FT-105; refractive index 1.555, average fiber diameter 13μ, manufactured by Asahi Fiber Glass Co., Ltd.

4) Polyoxyalkylene glycol Polyoxyethylene glycol PEG4000N (average molecular weight 3,000), Sanyo Chemical Co., Ltd. PEG2000 (average molecular weight 20,000), Sanyo Chemical Co., Ltd. 5) Polyoxyalkylene glycol poly Oxyethylene-polyoxypropylene-block copolymer Pronone 208, number average molecular weight 10,000, ethylene oxide 80% by weight, NOF CORPORATION Pronone 204, number average molecular weight 3,330, ethylene oxide 40 weight
%, NOF Corporation

6) Polyoxyethylene derivative Polyoxyethylene sorbitan monooleate Nonion OT-221, manufactured by NOF CORPORATION Polyoxyethylene bisphenol A (PEG-BP)
A) 7) Catalyst Titanium tetrabutoxide (monomer), abbreviated as TBT, manufactured by Wako Pure Chemical Industries, Ltd. 8) Heat stabilizer Adeka Stab PEP-36, manufactured by Asahi Denka Co., Ltd.

[Examples 1 to 3] The aromatic polycarbonate resin, polyoxyethylene glycol, and heat stabilizer were weighed in the amounts shown in Table 1 and thoroughly mixed with a tumbler. It was supplied from the first chute of a twin-screw extruder with a vent (TEM-35 manufactured by Toshiba Machine Co., Ltd.), and the glass fiber was supplied from the second chute in the middle of the extruder.
The mixture was melt-kneaded and pelletized at 0 ° C. The obtained pellets were dried at 120 ° C for 6 hours and then injection-molded at 260 ° C to obtain a physical property test piece. Tensile strength, flexural strength and flexural modulus were measured as mechanical properties, and Haze and total light transmittance were measured as optical properties. Table 1 shows the measurement results. Example 4 Aromatic polycarbonate resin, polyoxyethylene glycol, transesterification catalyst, heat stabilizer,
The amounts shown in Table 1 were weighed and pelletized in the same manner as in Example 1. The glass fiber was supplied from the second chute in the middle of the extruder as in Example 1. Physical property test pieces were obtained from the obtained pellets in the same manner as in Example 1, and the physical properties and the like were measured. Table 1 shows the measurement results.

Example 5 Aromatic polycarbonate resin, polyoxyalkylene glycol containing 80% by weight of polyoxyethylene glycol (Pronone 208), and heat stabilizer were weighed in the amounts shown in Table 1, respectively. Pelletized as in 1. The glass fiber was supplied from the second chute in the middle of the extruder as in Example 1. Physical property test pieces were obtained from the obtained pellets in the same manner as in Example 1, and the physical properties and the like were measured. Table 1 shows the measurement results. [Example 6] Aromatic polycarbonate resin, polyoxyethylene sorbitan monooleate, and heat stabilizer were weighed in the amounts shown in Table 1, respectively, in the same manner as in Example 1,
Pelletized. The glass fiber was supplied from the second chute in the middle of the extruder as in Example 1. Physical property test pieces were obtained from the obtained pellets in the same manner as in Example 1, and the physical properties and the like were measured. Table 1 shows the measurement results. [Example 7] Aromatic polycarbonate resin, polyoxyethylene bisphenol A (PEG-BPA), and a heat stabilizer were weighed in the amounts shown in Table 1 to give Example 1.
Pelletized as in. The glass fiber was supplied from the second chute in the middle of the extruder as in Example 1. Physical property test pieces were obtained from the obtained pellets in the same manner as in Example 1, and the physical properties and the like were measured. Table 1 shows the measurement results.

[Comparative Examples 1 to 3] The aromatic polycarbonate resin and the heat stabilizer were weighed in the amounts shown in Table 1 and pelletized in the same manner as in Example 1. The glass fiber was supplied from the second chute in the middle of the extruder as in Example 1. Physical property test pieces were obtained from the obtained pellets in the same manner as in Example 1, and the physical properties and the like were measured. Table 1 shows the measurement results.
Shown in [Comparative Example 4] Pelletization was performed in the same manner as in Example 5 except that pronone 204 was used instead of pronone 208. The glass fiber was supplied from the second chute in the middle of the extruder as in Example 5. Physical property test pieces were obtained from the obtained pellets in the same manner as in Example 5, and the physical properties and the like were measured. Table 1 shows the measurement results.

[0033]

[Table 1]

[0034]

EFFECT OF THE INVENTION The aromatic polycarbonate resin composition of the present invention has a high rigidity, a high elastic modulus, and excellent transparency, and has a transparent structure in the fields of automobiles, electric / electronic fields, building materials, etc. It can be used as a material and is extremely useful.

Claims (5)

[Claims] 1. 100 parts by weight of an aromatic polycarbonate resin, 1 to 150 parts by weight of glass fiber having a difference in refractive index from the aromatic polycarbonate resin of 0.015 or less, and 50% by weight of a polyoxyethylene glycol component. An aromatic polycarbonate resin composition comprising 1 to 40 parts by weight of a polyoxyalkylene glycol or polyoxyethylene derivative containing the above. 2. A polyoxyethylene glycol component of 5
The aromatic polycarbonate resin composition according to claim 1, wherein the polyoxyalkylene glycol containing 0% by weight or more has a number average molecular weight of 200 to 50,000. 3. A polyoxyethylene glycol component of 5
Polyoxyalkylene glycol containing 0% by weight or more,
It is polyethylene glycol, The aromatic polycarbonate resin composition of Claim 1 or 2 characterized by the above-mentioned. 4. The aromatic polycarbonate resin composition according to claim 1, wherein the polyoxyethylene derivative is a sorbitan derivative of polyoxyethylene. 5. The polyoxyethylene derivative is a polyoxyethylene glycol derivative obtained by reacting one end or both ends of polyoxyethylene glycol with alcohol, fatty acid, bisphenol A, phenol or alkylated phenol. The aromatic polycarbonate resin composition according to claim 1, which is characterized in that.