JP3097933B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether (hereinafter sometimes referred to as PPE) resin and a polycarbonate (hereinafter sometimes referred to as PC).
The present invention relates to a resin composition containing a system resin.

[0002]

2. Description of the Related Art PPE resins are resins having high heat resistance and excellent dimensional stability and impact resistance. However, PPE resins alone have poor molding workability, and polystyrene, polyamide (nylon), etc. Is added to improve the moldability and used.

[0003] On the other hand, polycarbonate resins are excellent in molding workability, and are also excellent in impact resistance, dimensional stability and the like.
Although the heat resistance is relatively high, the heat deformation temperature is about 130 ° C. or more (measured under a load of 18.6 kg), and the heat resistance is required to be improved depending on the application.

[0004] When a resin composition is produced by blending both resins in order to take advantage of the excellent properties of PPE and PC, this resin composition lacks compatibility between the two resins.
This causes a problem of low mechanical strength.

[0005] It is an object of the present invention to provide a resin composition in which a PPE-based resin and a polycarbonate-based resin are well compatible with each other and have excellent mechanical strength.

[0006]

The resin composition of the present invention comprises:
(A) 2 to 98 parts by weight of a polyphenylene ether resin, and (B) a (a) maleimide group and (b)
The following formulas -C (= O) -Cl, -C (= O) -Br, -C
A compound having at least one group selected from (＝ O) —OH, —OH, —O—C (＝ O) —Cl and —O—C (＝ O) —Br is copolymerized with a copolymer component or end-blocked. It contains a polycarbonate-based resin or 98 to 2 parts by weight of a polycarbonate-based resin and a polycarbonate-based resin.

First, in the present invention, known PPE resins can be used. The PPE resin is, for example, a compound represented by the general formula (Chemical Formula 1):

[0008]

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and at least 2
Represents a monovalent substituent selected from haloalkyl groups or haloalkoxy groups having three carbon atoms and not containing a tertiary α-carbon, and n is an integer representing the degree of polymerization. It is a generic term and may be a single polymer of the general formula or a copolymer of two or more. In a preferred embodiment, R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. For example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4) -
Phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-
6-propyl-1,4-phenylene) ether, and the like. Examples of the PPE copolymer include copolymers in which the above-mentioned polyphenylene ether repeating unit partially contains an alkyl trisubstituted phenol, for example, 2,3,6-trimethylphenol. In addition, these PPE
It may be a copolymer in which a styrene compound is grafted. The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing, for example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene or the like as the styrene-based compound on the above-mentioned PPE.

The polycarbonate resins used in the present invention include copolyester carbonates and the like in addition to conventionally known aromatic polycarbonates.

[0010] The polycarbonate contains a carbonate component and a diphenol component. Examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate. Suitable diphenols may have a heteroatom and may have a substituent that is inert under the conditions of polycarbonate production and inert to the influence of electromagnetic waves. Both mononuclear and polynuclear diphenols. For example, hydroquinone, resorcin, dihydroxydiphenyl, bis
-(Hydroxyphenyl) -alkane, bis- (hydroxyphenyl) -cycloalkane, bis- (hydroxyphenyl)-
Sulfide, bis- (hydroxyphenyl) -ether, bis- (hydroxyphenyl) -ketone, bis- (hydroxyphenyl) -sulfoxide, bis- (hydroxyphenyl) -sulfone and α, α′-bis- (hydroxyphenyl)-
Mention may be made of diisopropylbenzene and their ring-alkylated and ring-halogenated compounds.

Preferred diphenols are:
4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A),
2,4'-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, α, α'-bis- (4-hydroxyphenyl) -p-diisopropylbenzene, 2 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis- (3,5-dimethyl-4-hydroxyphenyl) methane, 2 , 2-bis- (3,5-dimethyl-4
-Hydroxyphenyl) propane, bis (3,5-dimethyl)
-4-hydroxyphenyl) sulfone, 2,4-bis- (3,5-
Dimethyl-4-hydroxyphenyl) -2-methylbutane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, α, α′-bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis ( 3,5-dichloro-4-hydroxyphenyl) propane, 2,
2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

Examples of particularly suitable diphenols are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (3,5-
Dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane. Any preferred combinations of the above diphenols can also be used. In addition to the above-mentioned monomeric diphenols, it is also possible to use oligomers or polymers having two terminal groups which can undergo a polymerization reaction under the conditions of the synthesis of the polycarbonate incidentally. Such terminal groups are, for example, phenolic OH groups, chlorocarbonate groups and carboxylic acid chloride groups. Pre-prepared oligomeric or polymeric blocks which already have such reactive groups or are capable of generating such groups by suitable work-up are, for example, polysiloxanes, for example hydrogenated 2 Polycondensates based on aliphatic diols and saturated aliphatic or aromatic dicarboxylic acids, such as saturated aliphatic polyesters based on dimeric fatty acids, aromatic polyether sulfones and aliphatic polyethers. For improving the flowability, trifunctional or higher-functional compounds in small amounts, preferably in an amount of 0.05 to 2.0 mol% (relative to the number of moles of diphenol used), In particular, compounds having three or more phenolic hydroxyl groups can also be used incidentally in a known manner.

Some examples of usable compounds having three or more phenolic hydroxyl groups are 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4 -Hydroxyphenyl) -ethane, 2,6-bis- (2-hydroxy-5-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl)- Ortho terephthalate, tetra- (4-hydroxyphenyl)-
Propane, hexa- (4- (2- (4-hydroxyphenyl) -prop-2-yl) -phenyl) -orthoterephthalate, tetra- (4-hydroxyphenyl) -methane and 1,4-
Bis (4 ′, 4 ″ -dihydroxy-triphenyl) -methyl) -benzene. Some other trifunctional compounds are:
2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis- (4-hydroxy-3-methylphenyl) -2-oxo-2,3-dihydro-indole.

As the copolyestercarbonate, in particular, the following formula (Formula 2):

[0015]

Embedded image And the following formula (Formula 3):

[0016]

Embedded image In the above formula, R and R 'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbonoxy group, and W is a divalent hydrocarbon group, -S-, -SS-, -O
-, -S (= O)-,-(O =) S (= O)-, or -C (= O)-, and n and n 'are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, b is 0 or 1, and has a structural unit represented by the formula: ) And 2 to 30 of the total amount of the structural units of
Copolyester carbonates which account for mole% are preferred. Examples of the halogen atom in the above formula include a chlorine atom and a bromine atom. Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a decyl group; a cycloalkyl group having 4 to 8 carbon atoms, such as a cyclopentyl group and a cyclohexyl group. An aryl group having 6 to 12 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group; an aralkyl group having 7 to 14 carbon atoms, such as a benzyl group or a cinnamyl group; or an alka group having 7 to 14 carbon atoms Examples include a reel group, for example, a tolyl group and a cumenyl group, and preferably an alkyl group. Examples of the hydrocarbon group of the hydrocarbon oxy group include the aforementioned hydrocarbon groups. Such a hydrocarbon oxy group is an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group or an alkaryloxy group, and an alkoxy group and an aryloxy group are preferred. When W is a divalent hydrocarbon group, an alkylene group having 1 to 30 carbon atoms, for example, a methylene group,
An ethylene group, a trimethylene group, an octamethylene group, etc., an alkylidene group having 2 to 30 carbon atoms, such as an ethylidene group, a propylidene group, or a cycloalkylene group having 6 to 16 carbon atoms, such as a cyclohexylene group,
A cyclododecylene group or a cycloalkylidene group,
For example, it is a cyclohexylidene group.

The structural unit represented by the above formula (Formula 3) comprises a diphenol component and a diacid component. For the introduction of the diphenol component, the same diphenol as described above can be used. The monomer used to introduce the diacid component is a diacid or an equivalent thereof. The divalent acid is, for example, an aliphatic diacid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The divalent acid or its equivalent may be linear, branched, or cyclic. The aliphatic diacid is preferably α, ω-dicarboxylic acid. As such a divalent acid, for example, straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decandioic acid), dodecandioic acid, tetradecandioic acid, icodecandioic acid, and the like are preferable, and sebacic acid and dodecane acid are preferable. Diacids are particularly preferred. Examples of the equivalent substance include the above-mentioned divalent acids, for example, acid halides such as acid chloride, and diaromatic esters such as diphenyl ester. However, the carbon number of the ester portion of the ester is not included in the carbon number of the acid described above. The above divalent acid or its equivalent may be used alone or in combination of two or more.

The above copolyestercarbonate is
It has the above-mentioned two types of structural units represented by (Chemical Formula 2) and (Chemical Formula 3) in the following proportions. That is, the amount of the structural unit represented by (Chem. 3) is 2 times the total amount of (Chem.
-30 mol%, preferably 5-25 mol%, more preferably 7-20 mol%.

The weight average molecular weight of the copolyestercarbonate is usually 10,000 to 100,000, preferably 18,000 to 4
It is 0,000. Here, the weight average molecular weight is defined as GP weight using polystyrene corrected for polycarbonate.
C (gel permeation chromatography). Further, those having an intrinsic viscosity of 0.35 to 0.65 dl / g measured at 25 ° C. in methylene chloride are preferred.

The above copolyester carbonate can be produced by a known polycarbonate production method, for example, an interfacial polymerization method using phosgene, a melt polymerization method, or the like. For example, it can be prepared by the methods described in US Pat. No. 4,238,596 to Quinn and US Pat. No. 4,238,597 to Quinn and Markezich. Specifically, first, an acid halide is formed prior to the reaction between the ester-forming group and the diphenol, and then reacted with phosgene. Goldberg (Goldb
erg) basic solution method (US Pat. No. 3,169,121)
In this, a pyridine solvent can be used, and a dicarboxylic acid is used. α, ω-dicarboxylic acid (eg sebacic acid)
A melt polymerization method using a diester of (for example, diphenyl ester) can also be used. A preferred production method is
U.S. Pat.No. 4,286,083 discloses Kochanowski.
nowski). In this method, a lower diacid such as adipic acid is converted into a salt form (preferably an alkali metal salt such as a sodium salt) in advance, and is added to a reaction vessel in which diphenol is present. During the reaction with phosgene, the aqueous phase is brought to an alkaline pH, preferably between about pH 8 and
9 and then a minimum of about 5 for the remaining reaction with phosgene.
At%, raise the pH to 10-11.

In the case of an interfacial polymerization method, for example, a bischloroformate method, it is preferable to use a general catalyst system well-known in the synthesis of polycarbonate and copolyestercarbonate. Primary catalyst systems include amines such as tertiary amines, amidines or guanidines. Tertiary amines are commonly used, of which trialkylamines such as triethylamine are particularly preferred.

Further, the above-mentioned polycarbonate resin may be used as a terminal blocking agent for adjusting the molecular weight, for example, phenol, pt-butylphenol, isononylphenol, isooctylphenol, m- or p-cumylphenol (preferably p-cumylphenol). Cumylphenol) and chromanyl compounds.

In the present invention, (a) a carbon-carbon double bond and
(b) The following formulas -C (= O) -Cl, -C (= O) -Br,-
At least one selected from C (= O) -OH, -OH, -OC (= O) -Cl and -OC (= O) -Br
A polycarbonate containing a compound having a certain group as a copolymer component or a terminal blocking agent, that is, a polycarbonate resin having a carbon-carbon double bond in its structure is used. In particular, polycarbonates whose terminals are blocked with such compounds and which have a double bond at the terminal are preferred. Such a polycarbonate-based resin having a double bond can be obtained by allowing the above-described compound to be present when a polycarbonate-based resin is produced by polymerizing a precursor of the above-mentioned carbonate component and diphenol. Such compounds include, for example, acrylic acid,
Unsaturated monoaliphatic carboxylic acids such as methacrylic acid, crotonic acid, oleic acid and linoleic acid and maleimide benzoic acid and their acid halides; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and their acid halogens Compounds such as isopropenyl phenol, allyl phenol, maleimide phenol and the like, and halogenocarbonates thereof. These can be used alone or as a mixture. In order to produce a polycarbonate obtained by copolymerizing the above compound at the terminal, among the above-mentioned compounds, unsaturated monoaliphatic carboxylic acid maleimide benzoic acid and acid halides thereof; isopropenyl phenol, allyl phenol, maleimide phenol and the like and It is preferable to use halogenocarbonates of the formula (1).

The compound serving as the above-mentioned copolymer component or terminal blocking agent is usually used in an amount of 0.001 to 0.2 mol, preferably 0.002 to 0.2 mol, per 1 mol of the raw material diphenol.
Add 1 mol.

Component (B) is used in an amount of 98 to 2 parts by weight, preferably (A) 30 to 70 parts by weight, based on 2 to 98 parts by weight of component (A).
(B) 70 to 30 parts by weight is blended with respect to parts by weight.
When the amount of (B) is less than 2 parts by weight, the improvement of the moldability of (A) is insufficient, while when the amount of (A) is less than 2 parts by weight, the improvement of the heat resistance of (B) is insufficient. .

As the component (B) in the present invention, only the above-mentioned polycarbonate resin having a double bond is used, or both the polycarbonate resin and a conventional (unmodified) polycarbonate resin are used. The mixing ratio of both is as follows: polycarbonate resins having a double bond at the terminal: 1 to 10
0 parts by weight of conventional polycarbonate resin 0-9
9 parts by weight. Preferably, the amount is from 0 to 80 parts by weight of a conventional polycarbonate-based resin to 20 to 100 parts by weight of a polycarbonate-based resin having a double bond at a terminal.

The resin composition of the present invention may contain, if desired, various additives such as other resins, elastomers, flame retardants, flame retardant assistants, stabilizers, ultraviolet absorbers, plasticizers, lubricants, pigments, fillers, Other components can be appropriately blended.

As other resins, (A) a resin having good compatibility with the PPE resin, for example, polystyrene, (B) a resin having good compatibility with polycarbonate, for example, polyester,
ABS resin and the like.

Elastomers are elastomers in a general sense and are described, for example, by AV Tobolsky, "Properties and Structures of Polymers (Prope
rties and Structures of Polymers) '' (John Vlley &
SonsInc., 1960) 71 can cite the definition set forth on pages to 78, elastomer and Young's modulus at room temperature is ¹⁰⁵ to
^A polymer that is ⁹ dynes / cm ² (0.1 to 1020 kg / cm ² ). Specific examples of the elastomer include ABA
-Type elastomeric block copolymer, ABA type elastomeric block copolymer in which double bonds of polybutadiene portion are hydrogenated, polybutadiene, polyisoprene,
Copolymer of diene compound and vinyl aromatic compound, nitrile rubber, ethylene-propylene copolymer, ethylene-
Propylene-diene copolymer (EPDM), thiocol rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, grafted product of butyl rubber and polyethylene,
Examples thereof include polyester elastomers and polyamide elastomers. In particular, an ABA type elastomeric block copolymer is preferable.

Examples of the various additives include flame retardants such as triphenyl phosphate, tricresyl phosphate, phosphate obtained from a mixture of isopropylphenol and phenol, and bifunctional compounds such as benzohydroquinone and bisphenol A. Phosphoric acid esters such as phosphates obtained from phenol and other alcohols or phenols; brominated compounds represented by decabromobiphenyl, pentabromotoluene, decabromobiphenyl ether, hexabromobenzene, brominated polystyrene, etc .; melamine Examples include nitrogen-containing compounds such as derivatives.

A flame retardant aid may be used, and examples thereof include antimony, boron, zinc and iron compounds.

Further additives include stabilizers such as sterically hindered phenols and phosphite compounds; ultraviolet absorbers exemplified by oxalic acid diamide compounds and sterically hindered amine compounds; exemplified by polyethylene wax, polypropylene wax and paraffin. And the like.

Further, pigments exemplified by titanium oxide, zinc sulfide, and zinc oxide; glass fibers, milled fibers,
Mineral fillers exemplified by glass beads, asbestos, wollastonite, mica, talc, clay, calcium carbonate, magnesium hydroxide, silica, potassium titanate fiber, diatomaceous earth, rock wool; aluminum and zinc flakes or brass And inorganic fillers represented by fibers of metals such as aluminum and zinc; and organic fillers represented by carbon fibers.

The method for producing the resin composition of the present invention is not particularly limited, but a method such as mixing and kneading the components with a mixer or the like at a temperature of 250 to 350 ° C. using an extruder or a kneader is used. Can be.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

The following compounds were used in the examples. Component (A) PPE: intrinsic viscosity (chloroform, 30 ° C) 0.46 dl /
g of poly (2,6-dimethyl-1,4-phenylene) ether Component (B) PC: polycarbonate of bisphenol A, trademark LE
XAN (manufactured by Nippon GE Plastics Co., Ltd.), intrinsic viscosity 0.46 dl / g PC-1 measured in methylene chloride at 25 ° C. PC-1: Polycarbonate having a double bond at a terminal portion manufactured as follows: To a mixture of 6 liters of ion-exchanged water and 7 liters of methylene chloride, add 2,2-bis
2.28 kg (10.0 mol) of-(4-hydroxyphenyl) -propane (ie bisphenol A), 75.6 g (0.4 mol) of N- (p-hydroxyphenyl) maleimide
And 14.0 ml of triethylamine were added, followed by vigorous stirring at room temperature. Next, an aqueous sodium hydroxide solution (5
Phosgene was blown into this mixed solution at a rate of 60 g / min for 20 minutes while maintaining the pH of the solution at 10. After the addition of phosgene, the mixture was stirred for 5 minutes, and then the methylene chloride solution and the aqueous phase were separated. After washing the methylene chloride solution with water, then with 2% hydrochloric acid and then again with water, the solvent was removed and the remaining product was dried at 100 ° C. overnight.

When the obtained product was analyzed by IR, absorption of ν _{C = O} was observed at 1704 cm ⁻¹ . Also, H
^{From 1} NMR measurement, a peak corresponding to a hydrogen atom bonded to the double bond carbon of the maleimide was found at δ 6.85 ppm. According to the molecular weight measurement by GPC, the number average molecular weight of this product was 11,300, the weight average molecular weight was 28,
It turned out to be 100. Component (B) PC-2: N- (p-hydroxyphenyl) maleimide
Instead of 5.6 g, 28.16 g (0.15 mol) of N- (p-hydroxyphenyl) maleimide and 14.0 of phenol were used.
A polycarbonate having a double bond at the terminal was produced in the same manner as in PC-1 except that g was used.

According to the molecular weight measurement by GPC, the number average molecular weight of this product was 13800 and the weight average molecular weight was 33.
It turned out to be 600. Optional components SEBS: KRATON G 1651 (trademark, manufactured by Shell Chemical Co., Ltd.), hydrogenated styrene-ethylene-butadiene-styrene copolymer Examples 1 to 6 and Comparative Examples 1 to 4 Weight ratio)
The mixture was extruded with a twin-screw extruder (30 mm) set at 299 ° C. and 300 rpm to produce pellets. Set the pellet at a set temperature of 29.
A test piece was prepared by injection molding at 9 ° C. and a mold temperature of 82 ° C.
For this, Izod impact strength, tensile strength, tensile elongation and gloss were measured. The results are shown in Tables 1 and 2.

The Izod impact strength was measured according to ASTM D256.
And the notched Izod impact strength was measured. Tensile strength and tensile elongation were measured according to ASTM D638. The gloss was measured at an incident angle of 60 ° and a reflection angle of 60 ° using a gloss meter.

[0040]

[Table 1] Table 1 ──────────────────────────────────── Example Comparative example Example Comparative example Example Comparative Example 1 1 2 2 3 3 Component (parts by weight) ) PC 80 90 50 65 27 35 PC-1 10-15-8-PPE 10 10 35 35 65 65 ────────────────────────── ────────── Izod impact strength (kg-cm / cm) 1/8 inch notch 83.8 69.1 7.1 1.6 1.1 1.1 1/8 inch notch 50.4 47.3 57.2 51.7 47.2 34.3 1/4 inch notch 11.3 11.9 4.3 4.3 1.1 1.6 1/4 inch Notch 9.8 10.3 5.4 1.6 28.3 1.6 Tensile strength (kg / cm ² ) 670 670 690 700 640 590 Tensile elongation (%) 84 101 57 27 4 3 ─────── ─────────────────────────────

[0041]

Table 2 ２ Example 4 Comparative Example 4 Example 5 Example 6 Component (parts by weight) PC 52 60 30 30 PC- 18-30-PC-2---30 PPE 32 32 32 32 SEBS 8 8 8 8 ──────────────────────────── ─────── Izod impact strength (kg-cm / cm) 1/8 inch Notch Room temperature 55.0 18.5 65.3 54.4-20 ℃ 41.6--36.7-30 ℃ 35.1-41.0 26.5-40 ℃ 19.4-24.8-1 / 4 inch Notch 53.5 22.1 50.2 55.1 Tensile strength (kg / cm ² ) 550 570 580 570 Tensile elongation (%) 85 50 61 78 Gloss 12.8 10.9 32.5 14.0 ────────────── ─────────────────────

[0042]

The resin composition of the present invention has excellent mechanical strength because PPE and PC are well compatible. Therefore, its use is wide and industrially useful.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 69/00 C08L 71/12

Claims (1)

(57) [Claims] 1. A polyphenylene ether resin (A)
2 to 98 parts by weight, and (B) maleimide in the molecule
Group and (b) the following formula -C (= O) -Cl, -C (= O)-
Br, -C (= O) -OH, -OH, -OC (= O)
Polycarbonate resin containing a compound having at least one group selected from —Cl and —O—C (＝ O) —Br as a copolymerization component or a terminal blocking agent, or 98 to 2 parts by weight of the polycarbonate resin and the polycarbonate resin A resin composition comprising: