JPH05279468A - Synthetic polymer-modifier and polycarbonate resin conposition containing the same - Google Patents

Abstract

PURPOSE:To provide the subject modifier comprising a specific block copolymer, excellent in antistaticity, transparency and appearance and useful for polycarbonates, etc. CONSTITUTION:The objective modifier comprises a block copolymer of formula I [A is polyoxyalkylene block comprising one or more kings of 2-4C oxyalkylene units: B is polyoxy-1,2-alkylene ether-1,2-alkylene carbonate block comprising one or more kinds of units of formula II (X<1>, Y<2> are ethylene, 1-6C hydrocarbon- substituted ethylene); (n) is 1-6; A block/B block = 10/90 to 90/10 (weight ratio)] having number-average mol.wt. of 1000-200000. 1-30wt.% of the modifier is added to 100 pts.wt. of a polycarbonate resin to give a polycarbonate resin composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a synthetic polymer modifier and a polycarbonate resin composition containing the same. Polycarbonate resin is a resin having excellent transparency, and is widely used for various purposes by taking advantage of its characteristics. However, the polycarbonate resin is likely to be charged like other thermoplastic resins, and dust and dirt are likely to be attached due to the charging.
Adhesion of dust and dirt to polycarbonate resin significantly reduces its commercial value because its characteristic is transparency. Therefore, it is strongly demanded that the polycarbonate resin should be antistatic while taking advantage of its characteristic transparency. The present invention relates to a synthetic polymer modifier and a polycarbonate resin composition containing the same, which meets such demands.

[0002]

2. Description of the Related Art Conventionally, a method applied to many other thermoplastic resins has been used to prevent the static charge of a polycarbonate resin. For this purpose, for example, 1) an example of using an inorganic conductive substance such as carbon black or metal powder, 2) an example of using a sulfonic acid type anionic surfactant such as an alkyl sulfonate or an alkylbenzene sulfonate (Japanese Patent Laid-Open No. Sho 5).
6-24442, JP-A-63-230764), 3) Examples using polyethers such as polyethylene oxide and polyoxyethylene-polyoxypropylene glycol ether (JP-B-55-4141), 4) Conjugated diene and polyalkylene glycol. Copolymer with acrylate,
It has a polyoxyalkylene glycol block such as a graft copolymer obtained by graft-polymerizing a vinyl monomer to a copolymer of a conjugated diene and polyalkylene glycol acrylate (JP-A-55-36237) and polyoxyalkylene ether ester amide. Examples include the use of block copolymers and graft copolymers. However, these conventional examples have inherent properties of the polycarbonate resin due to the inorganic conductive substance itself used or the poor compatibility or dispersibility of the compound and the polycarbonate resin used. There is a drawback that it impairs transparency and also impairs other physical properties.

[0003]

The problem to be solved by the present invention is that, in the conventional example, it is not possible to prevent the electrification while making the most of the physical properties inherent to the polycarbonate resin, especially the transparency.

[0004]

However, the present inventors have
As a result of earnest research from the above viewpoint, it is correct and preferable to use a block copolymer having a specific structure having a polyoxyalkylene block and a polyoxy1,2-alkylene ether-1,2-alkylene carbonate block in the molecule. Found.

That is, the present invention is a block copolymer represented by the following formula 1, wherein polyoxyalkylene block of A / polyoxy 1,2-alkylene ether-1,2-alkylene carbonate block of B = 10 / 9
A synthetic polymer modifier comprising a block copolymer having a ratio of 0 to 90/10 (weight ratio) and a number average molecular weight of 1,000 to 200,000, and 100 parts by weight of a polycarbonate resin. The present invention relates to a polycarbonate resin composition comprising 1 to 30 parts by weight of the synthetic polymer modifier.

[0006]

[Formula 1]

[In the formula 1, A: polyoxyalkylene block consisting of one or more oxyalkylene units having 2 to 4 carbon atoms B: one or more units of the unit represented by the following formula 2 Consisting of polyoxy 1,2-alkylene ether-1,2-
Alkylene carbonate block n: integer of 1 to 6]

[0008]

[Formula 2]

[In the formula 2, X ¹ and X ^{2 are} ethylene groups or ethylene groups simultaneously substituted with the same or different hydrocarbon groups having 1 to 6 carbon atoms]

In the block copolymer represented by the formula 1, one polyoxyalkylene block of A has one polyoxy 1,2-alkylene ether-1,2-alkylene carbonate block of B (hereinafter referred to as polyether carbonate block). One to six are combined.

The polyoxyalkylene block of A includes 1) a polyoxyalkylene block composed of a single oxyalkylene unit, such as a polyoxyethylene block, a polyoxypropylene block and a polyoxybutylene block, and 2) two or more kinds. There are mixed polyoxyalkylene blocks in which different oxyalkylene units are linked randomly or in blocks. The polyoxyalkylene block preferably contains 75 mol% or more of oxyethylene units, and more preferably 100 mol%. The number average molecular weight is 500 to 50.
000 is preferable, and 2000-40000 is more preferable.

As the polyether carbonate block of B, 1) polyoxyethylene ether ethylene carbonate block, 2) polyoxy 1,2-propylene ether-1,2-propylene carbonate block,
Polyoxy-1,2-n-butylene ether-1,2-
n-butylene carbonate block, polyoxy-1,
There are polyether carbonate blocks such as 2-isobutylene ether-1,2-isobutylene carbonate block, polyoxyphenylethylene ether phenylethylene carbonate block, and polyoxy-1,2-cyclohexene ether-1,2-cyclohexene carbonate block. As such a polyether carbonate block, a polyoxyethylene ether ethylene carbonate block is preferable.

The block copolymer used as the synthetic polymer modifier of the present invention is represented by the formula 1, and the ratio of the polyoxyalkylene block of A to the polyether carbonate block of B is 10/90. ~ 90/10
(Weight ratio) and the number average molecular weight (polystyrene molecular weight conversion value measured by GPC method) is 1000 to 20.
0000, preferably 5,000 to 100,000. When the proportion of the polyoxyalkylene block of A is higher than the above, the compatibility or dispersibility of the block copolymer with the polycarbonate resin is deteriorated, and the physical properties of the polycarbonate resin, particularly the transparency, are impaired. When the proportion of the polyoxyalkylene block of A is lower than the above, the antistatic effect obtained by such a block copolymer becomes low.

Next, a method for producing the block copolymer used as the synthetic polymer modifier of the present invention will be described. For example, there is a method in which 1,2-alkylene carbonate is subjected to ring-opening polymerization in the presence of a catalyst with respect to a polyether monool having one hydroxyl group in the molecule or a polyether polyol having 2 to 6 hydroxyl groups in the molecule. The polyether monool or polyether polyol used as a raw material is obtained by adding an alkylene oxide, specifically, ethylene oxide, propylene oxide, or 1,2-butylene oxide, to the active hydrogen compound, alone or in a mixture. The polyether monool is an alkylene oxide adduct of a monohydric alcohol or a monohydric phenol, and the polyether polyol is an alkylene oxide adduct of a divalent to hexavalent polyhydric alcohol or an alkylene oxide adduct of a divalent phenol. Can be advantageously used. 1,2
-As the catalyst used for the ring-opening polymerization of alkylene carbonate, a known catalyst, for example, an organometallic complex composed of a metal of Groups 2 to 4 of the periodic table having at least two alkoxy groups in the molecule can be advantageously used. ..

When 1,2-alkylene carbonate is reacted with the hydroxyl group of polyether monool or polyether polyol in the presence of a catalyst, usually 2 mol of 1,2-alkylene carbonate is obtained.
1 mol of carbon dioxide is released from the alkylene carbonate to give oxy-1,2-alkylene ether-1,
The 2-alkylene carbonate group is formed and the 1,2
-A ring-opening reaction and a ring-opening elimination reaction of alkylene carbonate occur alternately to form a polyoxy 1,2-alkylene ether-1,2-alkylene carbonate block, that is, a polyether carbonate block.

The end of the polyether carbonate block obtained by the above reaction usually becomes a hydroxyl group. In the present invention, such an end can be modified with an acyl group, an alkyl group or a silyl group. Specifically, 1) the terminal hydroxyl group is reacted with an acylating agent such as an organic monocarboxylic acid anhydride or an organic monocarboxylic acid halide to give an acylating terminal, and 2) the terminal hydroxyl group is an alkylating agent such as an alkyl halide. Can be reacted with the alkyl ether terminal, and the hydroxyl group at the 3) terminal can be reacted with a silyl etherifying agent such as trialkylchlorosilane, trialkylhydrogensilane, and trialkylsilanol to obtain the silyl ether terminal. Thus, when the terminal-modified product is melt-kneaded with the polycarbonate resin, it is possible to reduce undesired reactions such as transesterification and depolymerization of the polycarbonate resin.

The polycarbonate resin composition of the present invention contains 1 to 30 parts by weight, preferably 5 parts by weight, of the synthetic polymer modifier as described above per 100 parts by weight of the polycarbonate resin.
.About.25 parts by weight. When the content of the synthetic polymer modifier is less than 1 part by weight, the antistatic property is insufficient, and when it exceeds 30 parts by weight, the softening point temperature of the polycarbonate resin composition is lowered and the physical properties are deteriorated. Become.
Particularly, with respect to 100 parts by weight of the polycarbonate resin, in the block copolymer used as the synthetic polymer modifier, a polyoxyalkylene block composed of polyoxyethylene blocks / polyether carbonate block = 30 /
Those containing 5 to 25 parts by weight of the block copolymer in a ratio of 70 to 60/40 (weight ratio) have excellent antistatic properties while maintaining the original physical properties of the polycarbonate resin, particularly transparency.

When the synthetic polymer modifier of the present invention is added to the polycarbonate resin, both are melt-kneaded at a temperature higher than the melting point of the polycarbonate resin. In this case, the synthetic polymer modifier may be directly kneaded into the molten polycarbonate resin, or the master chip may be prepared in advance and then kneaded, whichever is good. Exhibits excellent kneadability (compatibility or dispersibility).

The polycarbonate resin used in the polycarbonate resin composition of the present invention is bisphenol A.
The basic skeleton is a polycarbonate synthesized by a condensation reaction of phosgene or diphenyl carbonate with phosgene or diphenyl carbonate, but it may be partially modified with bisphenol S or tetrabromobisphenol A. Further, the polycarbonate resin composition of the present invention may contain polystyrene, acrylonitrile-styrene copolymer, polyphenylene ether resin, or the like in the range of 50% by weight or less with respect to the polycarbonate resin. Further, the polycarbonate resin composition of the present invention may contain a stabilizer such as an antioxidant and an ultraviolet absorber in addition to various fillers, reinforcing fibers and pigments.

[0020]

【Example】

Test Category 1 (Synthesis of Block Copolymer Used as Synthetic Polymer Modifier) A block copolymer used as a synthetic polymer modifier was synthesized, and the block copolymer had a number average molecular weight and a polyoxyalkylene block / The proportions of the polyether carbonate block (weight ratio) are summarized in Table 1. These are measured as follows.

Number average molecular weight: The number average molecular weight in terms of polystyrene measured by gel permeation chromatography. Ratio of polyoxyalkylene block / polyether carbonate block (weight ratio): ¹ H-
It was calculated from the proton ratio by NMR. A / in Table 1
This is indicated by B.

Example 1 A flask was charged with 50 parts of polyethylene glycol having a number average molecular weight of 20,000 (parts by weight, the same applies hereinafter), and after substituting with nitrogen, sodium borohydride 0.1 was used as a catalyst.
Added parts. Heat to 200-210 ° C with stirring,
50 parts of ethylene carbonate was added dropwise over 2 hours.
After aging at this temperature for 4 hours, the mixture was cooled to room temperature to obtain 87.5 parts of a white block copolymer. The block copolymer was discharged onto a drum breaker to form flakes.

Example 2 In the same manner as in Example 1, using 30 parts of one-terminal methoxypolyethylene glycol having a number average molecular weight of 20,000, 70 parts of ethylene carbonate and 0.1 part of sodium pentaethoxy metastannate as a catalyst, a white powder was obtained. 82 parts of the block copolymer was obtained and was made into flakes.

Example 3 As in Example 1, 50 parts of polyethylene glycol having a number average molecular weight of 6000 and 50 parts of ethylene carbonate
Parts, 1,2-propylene carbonate 50 parts and sodium borohydride 0.1 part as a catalyst were used to obtain 126 parts of a white block copolymer, which was flaked.

Example 4 In the same manner as in Example 1, 10 parts of polyethoxylated diglycerin having a number average molecular weight of 2000, 90 parts of ethylene carbonate, and sodium borohydride as a catalyst of 0.
Using 1 part, 78 parts of a white block copolymer was obtained and flaked.

Example 5 In the same manner as in Example 1, using 80 parts of polyethoxylated trimethylolpropane having a number average molecular weight of 5000, 20 parts of ethylene carbonate and 0.1 part of sodium pentaethoxy metastannate as a catalyst, a white color was obtained. 95 parts of the block copolymer of was obtained, and this was made into flakes.

Example 6 100 parts of the block copolymer synthesized in Example 1 was charged into a flask, the atmosphere was replaced with nitrogen, and then 120 to 120% with stirring.
It heated at 130 degreeC and 0.7 part of acetic anhydride was dripped. After completion of dropping, the mixture was aged for 2 hours, and acetic acid by-produced under reduced pressure was removed to the outside of the system to obtain a terminal-modified block copolymer. This was flaked in the same manner as in Example 1.

Example 7 100 parts of the block copolymer synthesized in Example 4 was charged into a flask, the atmosphere was replaced with nitrogen, and then 120 to 120 with stirring.
It was heated to 130 ° C. and 3.5 parts of trimethylmethoxysilane was added dropwise. After completion of dropping, the mixture was aged for 2 hours, and by-produced methanol was removed under reduced pressure outside the system to obtain a terminal-modified block copolymer. This was flaked in the same manner as in Example 1.

[0029]

[Table 1]

Test Category 2 (Preparation of Polycarbonate Resin Composition and Evaluation of Molded Products Obtained Using the Same) Test Category 1 for 100 parts by weight of polycarbonate resin
The block copolymers and the like synthesized in Section 2 were blended as shown in Table 2. This was melt-kneaded at a resin temperature of 280 ° C. with a vented 40 mmφ extruder and extruded to form pellets. Next, the pellets were molded by an injection molding machine at a cylinder temperature of 230 ° C and a mold temperature of 60 ° C. Then, the physical properties of the molded product were measured and the condition thereof was evaluated as follows, and the results are summarized in Tables 3 and 4.

Tensile Strength: ASTM D638 Flexural Strength, Flexural Modulus: ASTM D790 Izod Impact Strength: ASTM D256-56A, shown in Table 3 as Izod.

Surface resistivity: 2 mmt × 80 mmφ molded product
It was cut out into a disk shape and used as a test piece for measurement. After treating this test piece under the following condition 1 or condition 2, 23 ° C. × 5
The surface specific resistance was measured using a super insulation resistance meter SM-8210 type manufactured by Toa Denpa Kogyo KK in an atmosphere of 0% RH. Condition 1: The test piece was conditioned at 23 ° C. × 50% RH for 24 hours and then measured. Condition 2; the test piece was washed with a 1% aqueous solution of a detergent (trade name of Mama Lemon manufactured by Lion Oil and Fats Co., Ltd.), and then the detergent was thoroughly rinsed with distilled water to remove surface water, and further 23 ° C.
The humidity was measured at × 50% RH for 24 hours and then measured.

Appearance, transparency and delamination of the molded product: The molded product or its fracture surface was visually observed and evaluated according to the following criteria. Appearance: ○ ・ ・ ・ Homogeneous throughout △: Inhomogeneous areas are observed × ・ ・ ・ Many inhomogeneous areas are transparent: ○ ・ ・ ・ Completely transparent or almost completely transparent △ ・ ・・ Semitransparent × ・ ・ ・ Completely opaque Delamination: ○ ・ ・ ・ No delamination was observed △ ・ ・ ・ Slight delamination was observed × ・ ・ ・ Large delamination was observed

[0034]

[Table 2]

In Table 2, * 1: sodium dodecylbenzene sulfonate * 2: polyethylene glycol having a number average molecular weight of 150,000 * 3: styrene-acrylonitrile copolymer (trade name Estyrene AS-20 manufactured by Nippon Steel Chemical Co., Ltd.) * 4: Polystyrene (trade name Estyrene GP-20 manufactured by Nippon Steel Chemical Co., Ltd.)

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

As is apparent from the above, the present invention described above has an effect that excellent antistatic properties can be imparted without impairing the physical properties inherent to the polycarbonate resin, particularly the transparency.

Claims (3)

[Claims] 1. A block copolymer represented by the following formula 1, wherein polyoxyalkylene block of A / polyoxy 1,2-alkylene ether-1,2-alkylene carbonate block of B = 10/90 to 90 / 10
(Weight ratio) and its number average molecular weight is 100.
A synthetic polymer modifier comprising a block copolymer of 0-200000. [Formula 1] [In Formula 1, A: Polyoxyalkylene block consisting of one or more oxyalkylene units having 2 to 4 carbon atoms B: Polyoxy consisting of one or more units of the unit represented by the following Formula 2 1,2-alkylene ether-1,2-
Alkylene carbonate block n: integer of 1 to 6] [Formula 2] [In the formula 2, X ¹ and X ^{2 are} ethylene groups or ethylene groups simultaneously substituted with the same or different hydrocarbon groups having 1 to 6 carbon atoms] 2. The synthetic polymer modifier according to claim 1, wherein the terminal of the polyoxy 1,2-alkylene ether-1,2-alkylene carbonate block of B is modified with an acyl group, an alkyl group or a silyl group. 3. A polycarbonate resin composition comprising 1 to 30 parts by weight of the synthetic polymer modifier according to claim 1 or 2 with respect to 100 parts by weight of the polycarbonate resin.