JP2005113003A - Additive for polycarbonate resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive for a polycarbonate resin, capable of improving the processability of the polycarbonate resin by increasing its fluidity without affecting the physical characteristics, heat resistance, and appearance of the resin. <P>SOLUTION: The additive for a polycarbonate resin contains the compound of formula (I). In formula (I), A is a methylene group or a 2-4C oxyalkylene group; n is an integer of 1-10; X is a hydrogen atom, a hydroxy group, or a group described by -COOR wherein R is a 1-22C alkyl group; and m is an integer of 1-3. The polycarbonate resin composition contains the polycarbonate resin and the additive. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an additive for polycarbonate resin and a polycarbonate resin composition containing the same.

  Polycarbonate resins are widely used in fields such as OA (office automation) equipment, electrical / electronic equipment, automobiles, and architecture due to their excellent impact resistance, heat resistance, electrical properties, and the like.

  However, large molded parts such as OA equipment housings have poor resin flowability, require molding conditions of high temperature and high pressure, and are inferior in molding processability. For this reason, it has been desired to improve the moldability of the polycarbonate resin.

In general, dioctyl phthalate and tricresyl phosphate used as a plasticizer for vinyl chloride resin and the like can improve the fluidity of the polycarbonate resin, but the compatibility with the polycarbonate resin is poor, and the physical properties of the resin and Remarkably reduces heat resistance. Patent Document 1 describes trimellitic acid esters as plasticizers. These trimellitic acid esters have improved compatibility, but are still sufficiently satisfactory from the viewpoint of heat resistance. is not.
Japanese Patent Publication No. 6-57783

  An object of the present invention is to provide an additive for polycarbonate resin that can improve the flowability of the polycarbonate resin and improve the processability without adversely affecting the physical properties, heat resistance and appearance of the resin.

  The present invention relates to an additive for a polycarbonate resin containing a compound represented by the formula (I) (hereinafter referred to as an additive of the present invention), a polycarbonate resin, and a polycarbonate resin composition containing the additive of the present invention, In addition, a polycarbonate resin composition further containing a thermoplastic resin is provided.

[Wherein, A is a methylene group or an oxyalkylene group having 2 to 4 carbon atoms, n is a number of 1 to 10 (when A is an oxyalkylene group having 2 to 4 carbon atoms, n represents the average number of moles added) , X is a hydrogen atom, a hydroxyl group or a group represented by —COOR (R is an alkyl group having 1 to 22 carbon atoms), m represents an integer of 1 to 3, and a plurality of X and m may be the same or different. Also good. ]

  The additive of the present invention improves the flowability of the polycarbonate resin and can improve processability without adversely affecting the resin physical properties, heat resistance and appearance.

[Additive of the present invention]
The additive of the present invention contains a compound represented by formula (I) (hereinafter referred to as compound (I)).

  Compound (I) has the formula (II)

(In the formula, X and m have the above-mentioned meanings.)
A carboxylic acid represented by formula (III), a lower alkyl ester thereof or an anhydride thereof,
HO- (A) _n- OH (III)
(In the formula, A and n have the above-mentioned meanings.)
A compound represented by formula (IV)
ROH (IV)
(Wherein R has the above-mentioned meaning)
Can be obtained by reacting with a compound represented by the formula (I) using a metal catalyst such as dibutyltin oxide.

  As the carboxylic acid represented by the formula (II), its lower alkyl ester or its anhydride, trimellitic acid or its anhydride, phthalic acid or its anhydride, p-hydroxybenzoic acid or its carbon number 1 to 3 Examples include lower alkyl esters, trimellitic anhydride, phthalic anhydride, and methyl p-hydroxybenzoate are preferable, and trimellitic anhydride is more preferable.

  Examples of the compound represented by the formula (III) include alkylene diols having 1 to 10 carbon atoms, polyoxyalkylene glycols having 2 to 4 carbon atoms of an alkylene group and an average addition mole number of 1 to 10 oxyalkylene groups. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol having a number average molecular weight of 200 to 1000, polypropylene glycol having a number average molecular weight of 200 to 1000, poly having a number average molecular weight of 200 to 1000 Oxytetramethylene glycol is preferred.

  The number average molecular weight is a value calculated from the following formula using a hydroxyl value (measured based on JIS K0070).

Number average molecular weight = [(56.1 × functional group number) / hydroxyl value] × 1000
Examples of the compound represented by the formula (IV) include monohydric alcohols having 1 to 22 carbon atoms, preferably 6 to 14 carbon atoms.

  The compound (I) has a number average molecular weight of 500 or more, more preferably 500 to 2000, particularly 800 to 1500, and an acid value of 1.0 mgKOH / g, from the viewpoint of heat resistance during polycarbonate resin molding and oxidative decomposition of the resin. In particular, those having a concentration of 0.5 mgKOH / g or less are preferred.

  In addition, the number average molecular weight of compound (I) is a value measured by the measuring method described in the Example. The acid value is a value measured based on JIS K0070.

  The additive of the present invention preferably contains 90% by weight or more, more preferably 95% by weight or more of compound (I) from the viewpoint of obtaining sufficient fluidity and excellent moldability of the polycarbonate resin.

  In addition to compound (I), the additive of the present invention can contain unreacted components in the production of compound (I).

[Polycarbonate resin]
The polycarbonate resin used in the present invention is preferably an aromatic polycarbonate produced by a reaction between a dihydric phenol and a carbonate precursor. The reaction between the dihydric phenol and the carbonate precursor includes a solution method or a melting method. Specific examples include a reaction between the dihydric phenol and phosgene and a transesterification reaction between the dihydric phenol and diphenyl carbonate.

  Divalent phenols include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis. (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like can be mentioned. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in admixture of two or more. Particularly preferred dihydric phenols are those based on bis (hydroxyphenyl) alkanes, particularly bisphenol A.

  Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate and the like.

  The polycarbonate resin may have a branched structure, and 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxy) may be used as the branching agent. Phenyl) -1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid, 1,3-bis (o-cresol) and the like. Moreover, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, etc. are used for adjustment of molecular weight.

  Further, as the polycarbonate resin, a copolymer having a polycarbonate part and a polyorganosiloxane part, or a polycarbonate resin containing this copolymer can also be used. Further, the copolymer may be a polyester-polycarbonate resin obtained by conducting a polymerization reaction of polycarbonate in the presence of an ester precursor such as a bifunctional carboxylic acid such as terephthalic acid or an ester-forming derivative thereof. . Furthermore, various polycarbonate resins can be used by mixing them appropriately.

  The polycarbonate resin preferably has a viscosity average molecular weight of 10,000 to 100,000, particularly preferably 14,000 to 40,000, from the viewpoint of mechanical strength and moldability. Here, the viscosity average molecular weight (Mv) is a value measured by the measuring method described in Examples.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention contains the polycarbonate resin and the additive of the present invention, but may further contain a thermoplastic resin. Examples of the thermoplastic resin include at least one selected from a styrene resin, a polyester resin, and an acrylic resin, and a styrene resin and a polyester resin are preferable.

  Examples of the styrene resin used in the present invention include 20 to 100% by weight of monovinyl aromatic monomers such as styrene and α-methylstyrene, and 0 to 60% by weight of vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. %, And a polymer obtained by polymerizing a monomer or a monomer mixture composed of 0 to 50% by weight of other vinyl monomers such as maleimide and methyl (meth) acrylate copolymerizable therewith. Can be mentioned. Examples of these polymers include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), and the like.

  A rubbery polymer-modified styrene resin can also be preferably used as the styrene resin. This modified styrene resin is preferably an impact-resistant styrene resin in which at least a styrene monomer is graft-polymerized on a rubber polymer. Examples of rubber-modified styrenic resins include impact-resistant polystyrene (HIPS) in which styrene is polymerized on a rubbery polymer such as polybutadiene, ABS resin in which acrylonitrile and styrene are polymerized on polybutadiene, and methyl methacrylate and styrene on polybutadiene. There are polymerized MBS resins and the like, and rubber-modified styrene resins can be used in combination of two or more, and can also be used as a mixture with the above-mentioned styrene resin which is unmodified rubber.

  Examples of the polyester resin used in the present invention include terephthalic acid and ester-forming derivatives thereof, for example, aromatic dicarboxylic acids such as dimethyl terephthalate and terephthaloyl dichloride, and aliphatic diols having 2 to 10 carbon atoms such as ethylene glycol, 1 , 3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanediol, cyclohexanedimethanol, or long-chain glycol (with a molecular weight of about Up to 6000), for example, a polyester with at least one diol selected from poly (tetramethylene glycol) and the like. Suitable polyester resins are polyethylene terephthalate (PET), poly-1,4-butylene terephthalate, and the like.

  Examples of the acrylic resin used in the present invention include (meth) acrylic acid; (meth) acrylonitrile; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. And a polymer or copolymer of a monomer selected from (meth) acrylic acid esters such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. Here, (meth) acrylic acid means acrylic acid or methacrylic acid, and (meth) acrylonitrile means acrylonitrile or methacrylonitrile.

  The weight ratio between the polycarbonate resin and the thermoplastic resin in the composition of the present invention is preferably polycarbonate resin / thermoplastic resin = 100/0 to 50/50 from the viewpoint of processability, impact resistance and transparency. 100/0 to 60/40 is more preferable.

  The content of the additive of the present invention in the composition of the present invention is based on 100 parts by weight of the total amount of the polycarbonate resin and the thermoplastic resin from the viewpoint of obtaining sufficient flowability of the polycarbonate resin and excellent moldability. 0.1 to 10 parts by weight is preferable, and 1 to 5 parts by weight is more preferable.

  From the viewpoint of achieving the object of the present invention, the content of the polycarbonate resin in the composition of the present invention is preferably 50% by weight or more, and more preferably 70% by weight or more.

  In the polycarbonate resin composition of the present invention, other additives usually used for the polycarbonate resin can be appropriately blended as needed for the purpose of improving the appearance, antistatic, improving weather resistance, improving rigidity, etc. Is preferably 5% by weight or less.

  The polycarbonate resin composition of the present invention can be obtained by blending and kneading the additive of the present invention, the polycarbonate resin, and further thermoplastic resin and other additives in an appropriate ratio. Mixing and kneading at this time are premixed with a commonly used equipment such as a ribbon blender, a drum tumbler, etc., then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder. It can be performed by a method using a machine, a conida or the like. The heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 300 ° C. It should be noted that the components other than the polycarbonate resin and the thermoplastic resin can be added as a master batch which is previously melt-kneaded with these resins.

  The polycarbonate resin composition of the present invention is a pellet obtained by the above melt-kneading molding method, or using this pellet as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, It can be produced as various molded products by vacuum molding, foam molding, or the like.

  Molded articles obtained from the polycarbonate resin composition of the present invention include copiers, fax machines, televisions, radios, tape recorders, video decks, personal computers, printers, telephones, information terminals, refrigerators, microwave ovens and other office automation equipment, homes Examples include electrical appliances, housings for electrical and electronic equipment, and various parts.

  The present invention is characterized by using an additive for a polycarbonate resin containing a compound represented by the formula (I). By using this additive, the fluidity of the polycarbonate resin is improved, and the resin properties, Workability can be improved without adversely affecting the heat resistance and appearance. The reason why the effect of the present invention is manifest is not clear, but based on the result that the additive of the present invention has a structure in which an aromatic ring is introduced, the compatibility with the resin is excellent. It is considered that the effect of the present invention is manifested because the frictional resistance of the sheet is reduced.

In the following synthesis examples, the number average molecular weight was measured by GPC (gel permeation chromatography) under the following conditions.
Column: TSK PWXL + G4000PWXL + G2500PWXL (both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI or UV (210 nm)
Eluent: 0.2 mol / L phosphate buffer / acetonitrile (9/1)
Flow rate: 1.0 mL / min
Injection volume: 0.1 mL
Standard: Polyethylene glycol Synthesis example 1
In a 1 L four-necked flask, 192.0 g (1.0 mol) of trimellitic anhydride, 45.0 g (0.5 mol) of 1,4-butanediol, 379.0 g (2.4 mol) of n-decanol, catalyst Then, 0.31 g (0.05% by weight) of dibutyltin oxide was charged, and dehydration esterification reaction was performed under nitrogen blowing until the acid value became 0.5 mgKOH / g or less under the condition of 220 to 230 ° C. Then, in order to distill off excess n-decanol, topping was performed under the conditions of 180 ° C. and 0.4 kPa to obtain Additive 1 (number average molecular weight: 1034).

Synthesis example 2
In a 1 L four-necked flask, 192.0 g (1.0 mol) of trimellitic anhydride, 59.0 g (0.5 mol) of 1,6-hexanediol, 312.0 g (2.4 mol) of n-octanol, catalyst Then, 0.28 g (0.05% by weight) of dibutyltin oxide was charged, and the reaction and the subsequent treatment were performed under the same conditions as in Synthesis Example 1 to obtain Additive 2 (number average molecular weight: 950).

Synthesis example 3
In a 1 L four-necked flask, 177.6 g (1.2 mol) of phthalic anhydride, 240.0 g (0.6 mol) of polyethylene glycol having an average molecular weight of 400, 227.5 g (1.44 mol) of n-decanol, as a catalyst 0.32 g (0.05% by weight) of dibutyltin oxide was charged, and the reaction and subsequent treatment were performed under the same conditions as in Synthesis Example 1 to obtain Additive 3 (number average molecular weight: 976).

Synthesis example 4
In a 1 L four-necked flask, 510.0 g (0.6 mol) of polyoxytetramethylene glycol having an average molecular weight of 850, 191.5 g (1.26 mol) of methyl p-hydroxybenzoate, 0.70 g (0 of dibutyltin oxide as a catalyst) 1% by weight), and the ester exchange reaction was carried out under the same conditions as in Synthesis Example 1, and then excess methyl p-hydroxybenzoate was distilled off at 200 ° C. and 0.4 kPa to obtain additive 4 (Number average molecular weight: 1090) was obtained.

Synthesis example 5
In a 1 L four-necked flask, 192.0 g (1.0 mol) of trimellitic anhydride, 75.0 g (0.5 mol) of triethylene glycol, 312.0 g (2.4 mol) of n-octanol, and dibutyltin oxide as a catalyst 0.29 g (0.05 wt%) was charged, and the reaction and subsequent treatment were performed under the same conditions as in Synthesis Example 1 to obtain Additive 5 (number average molecular weight: 982).

Examples 1-7 and Comparative Examples 1-5
The additives 1 to 5 of the present invention obtained in Synthesis Examples 1 to 5 or the comparative additives 1 to 2 shown below are blended in the proportions shown in Tables 1 to 3 to 100 parts by weight of the resin component shown below, and extruded Machine (labor plast mill twin screw extruder, manufactured by Toyo Seiki Co., Ltd.), melt-kneaded at 260 ° C., and pelletized. In all Examples and Comparative Examples, 0.1 parts by weight of Irgafos 168 (manufactured by Ciba Specialty Chemicals) and 0.2 parts by weight of Irganox 1076 (manufactured by Ciba Geigy) were used as antioxidants. Each was blended. The obtained pellets were dried at 80 ° C. for 12 hours, and the performance was evaluated by the following method. The results are shown in Tables 1-3.

<Resin component>
・ PC single system: Polycarbonate resin, Toughlon A1900 (manufactured by Idemitsu Petrochemical Co., Ltd.)
PC / ABS alloy: polycarbonate resin, Toughlon A2200 (Idemitsu Petrochemical Co., Ltd./Santac AT-05 (manufactured by Nippon I & L Co., Ltd.) (mixing ratio shown in Table 2)
PC / PET alloy system: polycarbonate resin, Toughlon A2500 (Idemitsu Petrochemical Co., Ltd./MA523 (Mitsubishi Rayon Co., Ltd.) (mixing ratio shown in Table 3)
<Comparison additive>
Comparative additive 1: Dioctyl phthalate, molecular weight: 390
Comparative additive 2: n-octyl trimellitate, molecular weight: 546
<Performance evaluation method>
-Spiral flow length (SFL): Measured under conditions of molding temperature 280 ° C, mold temperature 80 ° C, wall thickness 2mm, width 10mm, injection pressure 110MPa, unit cm
Flexural modulus: conforms to ASTM D790 (test conditions: 23 ° C., 4 mm), unit MPa
Izod impact strength (IZOD): Conforms to ASTM D256, 23 ° C. (wall thickness 1/8 inch), unit kJ / m ²
Heat resistance stability test PC single system: YI (yellow index) was measured with a color meter (manufactured by Suga Test Instruments Co., Ltd.) and indicated by ΔYI before and after the test.

  PC / ABS alloy system and PC / PET alloy system: In the alloy system, when a large amount of silver is generated, the measurement value becomes invalid, and the state of the surface of the molded product was visually observed and evaluated in the following five stages.

5: No discoloration 4: Slight discoloration 3: Yellow discoloration 2: Discoloration to brown 1: Discoloration to brown near black • Viscosity average molecular weight of resin (Mv)
PC single system: The viscosity of the methylene chloride solution at 20 ° C. was measured with an Ubellose viscometer, and the intrinsic viscosity [η] was determined from the viscosity. It showed in.

[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83
PC / ABS alloy system: A resin pellet or molded product crushed into small pieces is left in acetone for a whole day and night, then the insoluble matter is filtered off, dissolved in methylene chloride, and then the insoluble matter is filtered off with a 100 mesh wire mesh. ΔMv was determined by the same method as for the PC alone system.

PC / PET alloy type: Resin pellets or molded product crushed into small pieces were subjected to Soxhlet extraction with methylene chloride for 6 hours, the extract was taken out, and ΔMv was determined by the same method as for the PC single type.
Appearance: Resin was retained for 15 minutes at an injection molding temperature of 300 ° C., and the color and the surface of the molded product were evaluated according to the following criteria.
○: No coloration, no silver generation Δ: No coloration, some silver generation X: Coloring, silver generation is remarkable

Claims (7)

An additive for polycarbonate resin containing a compound represented by the formula (I).

[Wherein, A is a methylene group or an oxyalkylene group having 2 to 4 carbon atoms, n is a number of 1 to 10 (when A is an oxyalkylene group having 2 to 4 carbon atoms, n represents the average number of moles added) , X is a hydrogen atom, a hydroxyl group or a group represented by —COOR (R is an alkyl group having 1 to 22 carbon atoms), m represents an integer of 1 to 3, and a plurality of X and m may be the same or different. Also good. ]   The additive for polycarbonate resin according to claim 1, wherein the compound represented by the formula (I) has a molecular weight of 500 or more and an acid value of 1.0 mgKOH / g or less.   A polycarbonate resin composition comprising a polycarbonate resin and the additive according to claim 1 or 2.   The polycarbonate resin composition according to claim 3, further comprising a thermoplastic resin.   The polycarbonate resin composition according to claim 3 or 4, wherein a weight ratio of the polycarbonate resin to the thermoplastic resin is polycarbonate resin / thermoplastic resin = 100/0 to 50/50.   The polycarbonate according to any one of claims 3 to 5, wherein the content of the additive according to claim 1 or 2 is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polycarbonate resin and the thermoplastic resin. Resin composition. The polycarbonate resin composition according to any one of claims 4 to 6, wherein the thermoplastic resin is at least one selected from a styrene resin, a polyester resin, and an acrylic resin.