Modifier for polycarbonate resin

Abstract

An object of the present invention is to provide a modifier for a polycarbonate resin having excellent antistatic properties.SOLUTION: A modifier (X) for polycarbonate resins, comprising an allyl ether or a C 1-3 alkyl ether (A) of an alkyleneoxide (alkylene having 2 to 3 carbon atoms) adduct (a) of a bisphenol compound (a0). The bisphenol compound (a0) is preferably at least one selected from the group consisting of bisphenol A and bisphenol F.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a modifier for polycarbonate resins. [Background technology]

[0002] In general, polycarbonate resins are resins with excellent mechanical and thermal properties. However, they must be molded at high temperatures, which poses the problem of discoloration. To address this problem, Patent Document 1 proposes a resin composition containing a fatty acid ester, a phosphorus stabilizer, and an aromatic polycarbonate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-204737 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0004] However, Patent Document 1 has insufficient antistatic properties and has problems such as peeling electrification, etc. An object of the present invention is to provide a modifier for polycarbonate resins that has excellent antistatic properties. [Means for solving the problem]

[0005] The present inventors have conducted extensive research to solve the above problems and have arrived at the present invention. That is, the present invention provides a modifier (X) for polycarbonate resins, which contains an allyl ether or an alkyl ether (A) having 1 to 3 carbon atoms of an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (a) of a bisphenol compound (a0). [Effects of the Invention]

[0006] The modifier (X) for polycarbonate resins of the present invention has the following effects. (1) Excellent antistatic properties. (2) It gives molded products with excellent color. (3) It gives molded products with excellent transparency. (4) It gives excellent fluidity to polycarbonate resin. DETAILED DESCRIPTION OF THE INVENTION

[0007] <Bisphenol compound (a0)> Examples of the bisphenol compound (a0) in the present invention include bisphenol A [2,2-bis(4-hydroxyphenyl)propane], tetramethylbisphenol A, tetrachlorobisphenol A, tetrabromobisphenol A, bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, bisphenol B [2,2-bis(4-hydroxyphenyl)butane], bisphenol C [2,2-bis(4-hydroxy-3-methylphenyl)propane], bisphenol E [1,1-bis(4-hydroxyphenyl)ethane], bisphenol F (dihydroxydiphenylmethane), bisphenol S [bis(4-hydroxyphenyl)sulfone], bisphenol AP [1,1-bis(4-hydroxyphenyl)-1-phenylethane], and bisphenol AF [2,2-bis(4-hydroxyphenyl)hexafluoropropane].

[0008] Of the above (a0), bisphenol A and bisphenol F are preferred, with bisphenol A being more preferred, from the viewpoint of fluidity and antistatic properties.

[0009] <Alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (a) of bisphenol compound (a0)> The alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (a) in the present invention is obtained by adding an alkylene oxide (alkylene having 2 to 3 carbon atoms) (sometimes abbreviated as AO) to the bisphenol compound (a0) by an addition reaction. The addition reaction can be carried out by a known method, for example, in the presence of an alkali catalyst (sodium hydroxide, potassium hydroxide, etc.) at a temperature of 100 to 200°C.

[0010] Examples of alkylene oxides (alkylene having 2 to 3 carbon atoms) (sometimes abbreviated as AO) include ethylene oxide (EO) and 1,2-propylene oxide (PO). Among alkylene oxides (alkylene having 2 to 3 carbon atoms), from the viewpoint of antistatic properties and transparency, EO alone or a combination of EO and PO is preferred, and EO alone is more preferred. When EO and PO are used in combination, the molar ratio [(EO) / (PO)] is preferably 50 / 50 to 99 / 1, and more preferably 70 / 30 to 95 / 5.

[0011] The number of moles of AO added per mole of the alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (a) is preferably 2 to 40, more preferably 4 to 30, and particularly preferably 6 to 20, from the viewpoints of hue, antistatic properties, and flowability. The number average molecular weight (Mn, molecular weight calculated as hydroxyl value) of the AO adduct (a) can be calculated from the hydroxyl value (unit: mgKOH / g) of (a). The hydroxyl value in the present invention is measured in accordance with JIS K 1557-1. Number average molecular weight (Mn) of (a) = 56100 × 2 / [hydroxyl value of (a)]

[0012] <Allyl ether or alkyl ether having 1 to 3 carbon atoms (A) of alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (a) of bisphenol compound (a0)> The ether (A) in the present invention is an allyl ether or an alkyl ether having 1 to 3 carbon atoms of the alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (a). Examples of alkyl ethers (alkyl having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms) include methyl ether, ethyl ether, n-propyl ether, and isopropyl ether.

[0013] The ether (A) can be produced by a known method, for example, by etherifying the hydroxyl group of the AO adduct (a) with an alkyl (alkyl having 1 to 3 carbon atoms) halide (methyl chloride, etc.) or an allyl halide (allyl chloride, etc.) in the presence (preferably in the presence of an excess) of an alkali metal hydroxide (sodium hydroxide, potassium hydroxide). In the above reaction, it is preferable to remove the salt produced and the residual alkali metal hydroxide by known methods such as separation, treatment with an adsorbent, filtration, etc.

[0014] The hydroxyl value (unit: mgKOH / g) of the ether (A) is preferably 1 to 10, more preferably 2 to 5, from the viewpoints of transparency and antistatic properties. The hydroxyl value (unit: mgKOH / g) of (A) can be adjusted, for example, by the number of moles of AO added in the AO adduct (a) and the etherification rate of the hydroxyl groups in the AO adduct (a).

[0015] The number average molecular weight (Mn) of the ether (A) is preferably 300 to 2,000, more preferably 350 to 1,500, and particularly preferably 400 to 1,000, from the viewpoints of antistatic properties and fluidity. In the present invention, the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured as polystyrene equivalent values ​​by the GPC method using a GPC measuring instrument (HLC-8120GPC, manufactured by Tosoh Corporation), columns (two TSKgel GMHXL columns and TSKgel Multipore HXL-M, manufactured by Tosoh Corporation), and a solvent (dimethylformamide).

[0016] <Modifier for polycarbonate resin (X)> The polycarbonate resin modifier (X) of the present invention contains an allyl ether or an alkyl ether having 1 to 3 carbon atoms (A) of an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (a) of the bisphenol compound (a0). The polycarbonate resin modifier (X) may contain the below-described additive (D) as needed, within the range that does not impair the effects of the present invention. Based on the weight of the polycarbonate resin modifier (X), the weight of (A) is preferably 90% by weight or more, and the weight of the additive (D) is preferably 10% by weight or less.

[0017] <Polycarbonate resin (E)> The polycarbonate resin (E) in the present invention is produced by reacting the bisphenol compound (a0) with a carbonic acid diester or phosgene. Examples of the carbonic acid diester include dialkyl carbonates (having 1 to 12 carbon atoms), such as dimethyl carbonate, diethyl carbonate, and diisopropyl carbonate. The polycarbonate resin (E) may be used alone or in combination of two or more.

[0018] <Polycarbonate resin composition (Y)> The polycarbonate resin composition (Y) of the present invention contains the polycarbonate resin modifier (X) and a polycarbonate resin (E). The weight ratio of the polycarbonate resin modifier (X) to the polycarbonate resin (E) [(X) / (E)] is preferably 0.1 / 99.9 to 15 / 85, more preferably 0.5 / 99.5 to 10 / 90, and particularly preferably 1 / 99 to 5 / 95, from the viewpoint of the balance of antistatic properties, fluidity, and transparency.

[0019] The polycarbonate resin composition (Y) may contain additives (D) as needed, provided that the effects of the present invention are not impaired. Examples of additives (D) include colorants (D1) (e.g., white pigments), release agents (D2) (e.g., butyl stearate), antioxidants (D3) (e.g., triphenyl phosphite), flame retardants (D4) (e.g., halogen-containing flame retardants), ultraviolet absorbers (D5) (e.g., phenyl salicylate), antibacterial agents (D6) (e.g., benzoic acid), compatibilizers (D7) (e.g., modified vinyl polymers), and fillers (D8) (e.g., talc). The total weight of the additives (D) based on the weight of the polycarbonate resin composition (Y) is preferably 20% by weight or less, and more preferably 0.01 to 5% by weight.

[0020] The polycarbonate resin composition (Y) is obtained by melt-mixing the modifier for polycarbonate resin (X), the polycarbonate resin (E), and, if necessary, the additive (D). As a method for melt mixing, a method can generally be applied in which each component is made into a pellet or powder form and mixed in an appropriate mixer (such as a Henschel mixer), and then melt mixed in an extruder and pelletized.

[0021] <Molded products> The molded article of the present invention is obtained by molding the polycarbonate resin composition (Y). Examples of molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, and film molding (casting method, tenter method, inflation method, etc.), and molding can be performed by any method incorporating means such as single-layer molding, multi-layer molding, or foam molding depending on the purpose. [Example]

[0022] The present invention will be further explained below with reference to examples, but the present invention is not limited to these examples. In the following examples, all parts are by weight.

[0023] Example 1 A stainless steel pressure-resistant reactor equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen inlet tube, and a pressure reducing device was charged with 800 g of a 2.1-mol ethylene oxide adduct of bisphenol A (a-1) [hydroxyl value-based molecular weight: 322, Hazen color unit: 10] and 257 g of sodium hydroxide beads. After replacing the atmosphere with nitrogen, 300 g of methyl chloride was added dropwise over approximately 1 hour with stirring, the temperature was raised to 85°C, and the reaction was continued for 10 hours. Next, 600 g of water was added with stirring to dissolve the produced salt, and then the stirring was stopped and the mixture was allowed to stand at 85° C. for 2 hours, after which the lower layer (aqueous layer) was removed. Furthermore, 16 g of Kyoward 600 (registered trademark) (manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an adsorbent, and the mixture was stirred at 120° C. for 30 minutes, and the contents were filtered. The resulting filtrate was placed in a stainless steel pressure reactor and dehydrated under reduced pressure at 100°C while stirring until the water content was 0.1% by weight or less, yielding a methyl ether of bisphenol A ethylene oxide adduct (A-1). The resulting ether (A-1) was designated as a polycarbonate resin modifier (X-1). The hydroxyl value of (A-1) was 4.8 and the number average molecular weight was 350.

[0024] <Examples 2 to 8> Each ether (A) was obtained in the same manner as in Example 1, except that the raw material (g) used in Table 1 was used. Each obtained ether (A) was designated as each polycarbonate resin modifier (X). The results are shown in Table 1.

[0025] <Comparative Example 1> For comparison, a commercially available 4-mol ethylene oxide adduct of nonylphenol was used as is to prepare a polycarbonate resin modifier (Comparative X-1) containing (Comparative A-1).

[0026] <Comparative Example 2> For comparison, commercially available bisphenol A was used as is to prepare a modifier for polycarbonate resins (Comparative X-2) containing (Comparative A-2).

[0027] <Comparative Example 3> For comparison, commercially available polyethylene oxide was used as is to prepare a modifier for polycarbonate resin (Comparative X-3) containing (Comparative A-3).

[0028] [Table 1]

[0029] <Examples 11 to 22 and Comparative Examples 11 to 14> Each polycarbonate resin composition (Y) was obtained by melt-kneading each raw material in a twin-screw extruder at 250°C and 80 rpm according to the raw materials (parts) used in Table 2. Each resin composition (Y) was molded using an injection molding machine (trade name "PS40E5ASE", Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 330°C and a mold temperature of 80°C to prepare the specified test pieces (molded products). The antistatic properties, color, and haze were measured using the following test methods. The results are shown in Table 2. Resin composition (Y) was injection-molded using an injection molding machine (trade name "PS40E5ASE", Nissei Plastic Industrial Co., Ltd.) equipped with a spiral flow test mold having a flow path 10 mm wide and 1 mm thick, under conditions of a cylinder temperature of 280°C, an injection pressure of 200 MPa, and a mold temperature of 100°C to produce a molded piece, and the spiral flow was measured using the following test method. The results are shown in Table 2.

[0030] <Raw materials used> [Polycarbonate resin (E)] (E-1): Commercially available polycarbonate [trade name "Panlite L-1225Y", manufactured by Teijin Limited]

[0031] <Test Method> (1) Antistatic property (unit: Ω / sq) In accordance with ASTM D257, the test piece (100 x 100 x 2 mm) was measured using a super insulation meter "DSM-8103" (manufactured by Toa Denpa Kogyo Co., Ltd.) in an atmosphere of 23°C and 50% RH.

[0032] (2) Hue The yellow index (YI) was measured using a color and turbidity simultaneous measuring instrument NIPPON DENSHOKU COH400 (manufactured by Nippon Denshoku Industries Co., Ltd.) The smaller the YI value, the more preferable it is.

[0033] (3) Haze (unit: %) A test piece (40 x 40 x 2 mm) was used and the measurement was carried out using a haze meter in accordance with JIS K7105 (1981).

[0034] (4) Spiral flow (unit: mm) The obtained molded pieces were used as test pieces for evaluating injection molding processability (fluidity). The distance flowed through the flow path of the spiral flow test mold was measured, and the longer the flow path length, the better the fluidity.

[0035] [Table 2]

[0036] The results in Tables 1 and 2 show that the modifier (X) for polycarbonate resins of the present invention has superior antistatic properties, provides excellent color and transparency to molded articles, and imparts excellent fluidity to polycarbonate resins, compared to the comparative modifiers. [Industrial Applicability]

[0037] The polycarbonate resin modifier of the present invention imparts excellent antistatic properties, color, transparency, and high fluidity to polycarbonate resin substrates, and molded articles obtained by molding resin compositions containing the resin modifier can be suitably used in a wide range of fields, such as for electrical and electronic devices, transport materials, daily necessities, and building materials.

Claims

1. A modifier (X) for polycarbonate resins, comprising an allyl ether or an alkyl ether (A) having 1 to 3 carbon atoms of an alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (a) of a bisphenol compound (a0).

2. 2. The polycarbonate resin modifier according to claim 1, wherein the bisphenol compound (a0) is at least one selected from the group consisting of bisphenol A and bisphenol F.

3. 2. The polycarbonate resin modifier according to claim 1, wherein the number of moles of the alkylene oxide (alkylene having 2 to 3 carbon atoms) adduct (a) added is 2 to 40.

4. 2. The polycarbonate resin modifier according to claim 1, wherein the ether (A) has a hydroxyl value (unit: mgKOH / g) of 1 to 10.

5. 2. The polycarbonate resin modifier according to claim 1, wherein the ether (A) has a number average molecular weight (Mn) of 300 to 2,000.

6. A polycarbonate resin composition (Y) comprising the modifier for polycarbonate resins (X) according to any one of claims 1 to 5 and a polycarbonate resin (E).

7. A molded article (Z) obtained by molding the polycarbonate resin composition (Y) according to claim 6.

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