JPH1046017A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition, excellent in flame retardance, rigidity and heat resistance. SOLUTION: This polycarbonate resin composition comprises 95-50wt.% of a polycarbonate resin and 5-50wt.% of glass fibers and is obtained by blending 100 pts.wt. of the polycarbonate resin with 0.5-10 pts.wt. of a phosphoric ester-based compound, 0.1-5 pts.wt. of a trihydrocarbyl (iso)cyanate, (iso)cyanuric acid or an alkali metallic (iso)cyanurate and 0-2 pts.wt. of a polytetrafluoroethylene having the fibril-forming ability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition reinforced with glass fibers.

[0002]

2. Description of the Related Art Polycarbonate resins have excellent mechanical properties and are widely used industrially in the fields of automobiles, office automation equipment, and electric and electronic fields. As the thickness of molded products such as products becomes thinner, materials having even higher strength and rigidity are required. On the other hand, in recent years, there has been a strong demand for synthetic resin materials to be made flame-retardant, mainly for applications such as OA equipment and home electric appliances, and a large number of flame retardants have been developed and studied to meet these demands. Usually, a halogen compound or the like is mainly used to make the polycarbonate resin flame-retardant, and in many cases, antimony trioxide or the like is additionally used as a flame-retardant auxiliary. When a halogen compound is blended with a synthetic resin as a flame retardant, the effect of flame retardation is relatively large, but it may cause environmental pollution at the time of fire or incineration, and may also impair mechanical properties or reduce molding time. It has problems such as discoloration, deterioration in physical properties and coloring when used for a long time at a high temperature.
For this reason, it is desired to reduce the amount of the halogen compound used.

In order to reduce the amount of halogenated compounds,
For example, a composition in which a thermoplastic resin such as an aromatic polycarbonate resin is mixed with an aromatic oligomeric phosphate ester is disclosed in JP-A-59-202240.
In order to obtain excellent flame retardancy, it is necessary to add a large amount of a phosphoric ester of an aromatic oligomer, so that there is a disadvantage that mechanical properties and thermal properties are impaired.

Japanese Patent Application Laid-Open No. 54-85242 discloses a composition in which melamine cyanurate is blended with a thermoplastic resin such as a polycarbonate resin, but the mechanical and thermal properties are insufficient. JP-A-4-50259 discloses a composition comprising a polycarbonate resin mixed with glass fibers and an adduct of melamine / cyanuric acid, but the dimensional stability is improved but the flame retardancy is insufficient. JP-A-3-115456 discloses a composition comprising an aromatic polycarbonate and at least one compound selected from the group consisting of trihydrocarbyl (iso) cyanurate, cyanuric acid and an alkali metal salt thereof. However, it is not always satisfactory in terms of flame retardancy and rigidity, and it is difficult to obtain a resin with excellent flame retardancy, heat resistance, and rigidity. Was Tsu.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polycarbonate resin composition having excellent flame retardancy and excellent rigidity and heat resistance.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and its gist is as follows.
(A) 95-50% by weight of polycarbonate resin and (B)
(C) 0.5 to 10 parts by weight of a phosphate compound based on 100 parts by weight of a polycarbonate resin, (D) trihydrocarbyl (iso) cyanurate, (iso) cyanur A polycarbonate resin composition comprising 0.1 to 5 parts by weight of an alkali metal salt of an acid or (iso) cyanuric acid and 0 to 2 parts by weight of (E) polytetrafluoroethylene having a fibril-forming ability.

Hereinafter, the present invention will be described in detail. The polycarbonate resin (A) in the present invention is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Examples of the dihydric phenol 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, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and the like. The dihydric phenol is preferably bis (4-hydroxyphenyl)
Alkanes, particularly those containing bisphenol A as a main raw material, may be mentioned. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate, and more specifically, phosgene, diphenyl carbonate, dihaloformate of divalent phenol, and a mixture thereof. In producing the polycarbonate resin, the dihydric phenol may be used alone or in combination of two or more.

Further, 0.01 to 3 mol%, preferably 0.1%, of a branching agent is added to the above dihydric phenol compound.
A combined use of about 1.0 mol% to about 1.0 mol% can give a branched polycarbonate, and phloroglysin, 2,6-dimethyl-2,4,6-tri (4
-Hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,1,3,5-tri (2-hydroxyphenyl) benzol, 1,1, 1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-
Methylbenzyl) -4-methylphenol, α, α ′,
α "-tri (4-hydroxyphenyl) -1,3,5-
Polyhydroxy compounds exemplified by triisopropylbenzene and the like, and 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol);
5-chlorisatin, 5,7-dichlorisatin, 5-
Bromoisatin and the like are exemplified.

The viscosity average molecular weight of the polycarbonate resin (converted from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent) is 10,000 to 100,000, and is preferably 1 to 100 from the viewpoint of moldability or physical properties of a molded article. 50,000 to 60,000. When producing a polycarbonate resin having these viscosity average molecular weight, a suitable molecular weight regulator,
A catalyst or the like for accelerating the reaction may be added.

[0010] As the glass fiber (B) in the present invention, any glass fiber which is usually used for a thermoplastic resin can be used, but alkali-free glass (E glass) is preferable. The diameter of the glass fiber is preferably 6-20μ
m, more preferably 9 to 14 μm. If the fiber diameter is less than 6 μm, the appearance of the molded article will be poor, and if it exceeds 20 μm, the reinforcing effect tends to be insufficient. As the glass fiber, any one of commercially available chopped strands cut to a length of 1 to 6 mm and milled fibers pulverized to a length of 0.01 to 0.5 mm may be used. You may use it. The glass fiber used in the present invention may be, for the purpose of improving the adhesion to the resin, a surface treatment with a silane coupling agent such as aminosilane or epoxysilane, or the like, or an acrylic resin, urethane for the purpose of improving the handleability. It may be used after performing a convergence treatment with a system resin or the like.

The mixing ratio of the glass fiber and the polycarbonate resin is 5 to 50% by weight of the glass fiber to 95 to 50% by weight of the polycarbonate resin. If the glass fiber content is less than 5% by weight or more than 50 parts by weight, the flame retardancy tends to decrease. The mixing ratio of the glass fiber and the polycarbonate resin is preferably 10 to 40% by weight of the glass fiber.
90 to 60% by weight of polycarbonate resin.

The (C) phosphate compound in the present invention includes, but is not limited to, a phosphate compound represented by the following general formula (1).

[0013]

Embedded image

In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, but R ¹ , R ² , R ³
And the case where R ⁴ is H. The organic group may be substituted, for example, an alkyl group, a cycloalkyl group,
And an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group,
Arylthio groups, halogenated aryl groups and the like,
Further, a group obtained by combining these substituents (eg, an arylalkoxyalkyl group) or a group obtained by combining these substituents by an oxygen atom, a sulfur atom, a nitrogen atom, or the like (eg, an arylsulfonylaryl group) is substituted. It may be a group.

X represents a divalent or higher valent organic group, and the divalent or higher valent organic group is a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above organic group. Is mentioned. Examples of the divalent or higher valent organic group include an alkylene group, a phenylene group which may have a substituent, a group derived from polynuclear phenols and bisphenols, and the like. The position is arbitrary. Particularly preferred examples of the divalent or higher valent organic group include hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, and dihydroxynaphthalene.

P is 0 or 1, q is an integer of 1 or more, preferably an integer of 1 to 30, r is an integer of 0 or more, preferably 1 to 10; When r is 0, at least one of R ¹ , R ³ and R ⁴ represents an organic group.

Examples of the phosphoric ester compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diisopropyl Phenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3-dibromopropyl) and bis (chloropropyl) monooctyl phosphate, R ¹ to R ⁴ is alkoxy such as methoxy, ethoxy and propoxy Or preferably (substituted) phenoxy, such as bisphenol A bisphosphate, which is phenoxy, methyl (substituted) phenoxy, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate, etc., preferably triphenyl phosphate and various bis It is a phosphate. These may be used alone or in combination of two or more.

The mixing ratio of the phosphate compound is 0.5 to 1 with respect to 100 parts by weight of the polycarbonate resin.
0 parts by weight. When the compounding ratio of the phosphate ester compound is less than 0.5 part by weight, the flame retardancy is insufficient, and when it exceeds 10 parts by weight, the heat resistance tends to decrease. The compounding ratio of the phosphate compound is preferably 1 to 6 parts by weight based on 100 parts by weight of the polycarbonate resin.

The trihydrocarbyl (iso) cyanurate in the present invention is obtained by substituting three protons of (iso) cyanuric acid with a hydrocarbyl group. Is a group such as alkyl, alkenyl, aryl, cycloalkyl, etc. obtained by removing one. The hydrocarbyl group may be unsubstituted or substituted with a stable substituent such as alkoxy, aryloxy or epoxyethyl. Examples of the unsubstituted hydrocarbyl group include a methyl, propyl, octyl, allyl, phenyl, and cyclohexyl group, and examples of the substituted hydrocarbyl group include a methoxyethyl and glycidyl group.

Preferred examples of the trihydrocarbyl (iso) cyanurate include triphenyl cyanurate (triphenoxy-1,3,5-triazine), triallyl isocyanurate and triglycidyl isocyanurate. In the present invention, the (iso) cyanuric acid and the alkali metal salt of (iso) cyanuric acid are preferably (iso) cyanuric acid itself, mono-, di- or tri-sodium salt of (iso) cyanuric acid and mono-cyanuric acid. ,
Di- or tri-potassium salts are included.

The mixing ratio of trihydrocarbyl (iso) cyanurate, (iso) cyanuric acid or an alkali metal salt of (iso) cyanuric acid is one part of the polycarbonate resin.
It is 0.1 to 5 parts by weight based on 00 parts by weight. Trihydrocarbyl (iso) cyanurate, (iso) cyanuric acid or an alkali metal salt of (iso) cyanuric acid is 0.1%
When the amount is less than 5 parts by weight, the flame retardancy is insufficient, and when it exceeds 5 parts by weight, the mechanical properties are apt to deteriorate. The mixing ratio of the trihydrocarbyl (iso) cyanurate, (iso) cyanuric acid or the alkali metal salt of (iso) cyanuric acid is preferably 0.5 to 4 parts by weight with respect to 100 parts by weight of the polycarbonate resin. .

The (E) polytetrafluoroethylene having a fibril-forming ability in the present invention has a tendency to be easily dispersed in a polymer and to form a fibrous material by bonding the polymers. Polytetrafluoroethylene having fibril-forming ability is classified into Type 3 according to ASTM standards. Examples of polytetrafluoroethylene having fibril-forming ability include Teflon 6J or Teflon 3 from Mitsui-DuPont Fluorochemicals Co., Ltd.
It is commercially available as 0J or as polyflon from Daikin Chemical Industries, Ltd.

The mixing ratio of polytetrafluoroethylene having a fibril-forming ability is 1% of the polycarbonate resin.
0 to 2 parts by weight based on 00 parts by weight. If the amount of polytetrafluoroethylene having fibril-forming ability exceeds 2 parts by weight, the appearance tends to deteriorate. The compounding ratio of polytetrafluoroethylene having a fibril-forming ability is preferably 0.01 to 1.5 parts by weight, more preferably 0.0 to 1.5 parts by weight, based on 100 parts by weight of the polycarbonate resin.
5 to 1.0 parts by weight. By blending a small amount of polytetrafluoroethylene having fibril-forming ability, the blending amount of other flame retardants can be reduced.

The polycarbonate resin composition of the present invention comprises
The above components can be manufactured by mixing with a mixer such as a tumbler, a V-type blender, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder, and the like. In the production of the polycarbonate resin composition of the present invention, the method of mixing the components and the order of mixing are not particularly limited. A preferred method is to, for example, previously mix each component other than the glass fiber in a tumbler, a V-type blender, or the like,
A method of melt-mixing with an extruder and supplying, mixing and pelletizing glass fibers from the middle of the extruder, or a method of mixing all components in advance by a tumbler, V-type blender, etc., and uniformly melt-mixing with an extruder. And the like.

In the polycarbonate resin composition of the present invention, various additives, such as stabilizers, release agents, ultraviolet absorbers, dyes and pigments, are added in amounts not to impair the effects of the present invention. Inorganic fillers other than glass fibers, other known flame retardants and the like can be contained. The physical properties of the polycarbonate resin composition of the present invention are as follows: ASTM D
The flexural modulus of 790 is 40000 kg / cm ² or more, and the flammability of 1/16 ″ thickness specified by UL94 is V-0.
And the deflection temperature under load at 1820 kPa of ASTM D648 is 120 ° C. or more. The polycarbonate resin composition of the present invention can be easily molded by a method such as extrusion molding, injection molding, or compression molding, and can be applied to blow molding, vacuum molding, gas injection molding, and the like, and has excellent flame retardancy. And electrical products, OA, which require reliability
It can be suitably used as a housing for equipment and the like, a chassis use, and a material for various parts.

[0026]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
However, unless the present invention exceeds the gist,
It is not limited to the example. Parts in the following examples
Represents parts by weight. Physical property evaluation was performed by the following measurement methods.
Was. (1) Flammability: 1/1 prepared according to UL standard 94
Using a 6 "thick test piece, UL standard 94 20mm vertical
A direct combustion test was performed. (2) Burning time: 20 mm vertical burning test of UL standard 94
At the time of total combustion after 5 samples
The interval was displayed in units of seconds. (3) Deflection temperature under load: According to ASTM standard D-648
A at 1820 kPa using the test piece
The test of STM D-648 was performed. Load deflection temperature
Is expressed in units of ° C. (4) Flexural modulus: according to ASTM standard D-790
Using the prepared bending test piece, ASTM D-790
A bending test was performed. Flexural modulus is kg / cm ^TwoSimply
Display in place. (5) Izod impact strength: ASTM standard D-256
ASTM D-
A 256 1/8 "notched impact test was performed.
Zod impact strength is expressed in kg · cm / cm.
You.

The raw materials used are as follows. (6) Polycarbonate resin (sometimes referred to as PC): Mitsubishi Engineering-Plastics Corporation
Manufactured by trade name Iupilon S-3000, viscosity average molecular weight 2
2,000. (7) Glass fiber: T5, manufactured by NEC Corporation
25. (8) Phosphate ester compound-1 (phosphate ester-
It may be referred to as 1. ): Condensed phosphate ester, trade name PX-200, manufactured by Daihachi Chemical Co., Ltd. (9) Phosphate ester compound-2 (phosphate ester-
It may be referred to as 2. ): Triphenyl phosphate, manufactured by Daihachi Chemical Co., Ltd., trade name: TPP.

(10) Cyanuric acid, manufactured by Wako Pure Chemical Industries, Ltd. (11) Triglycidyl isocyanurate, manufactured by Nissan Chemical Industries, Ltd., trade name TEPIC-S. (12) Melamine cyanurate, manufactured by Ogaki Chemical Co., Ltd., trade name MX44. (13) Polytetrafluoroethylene having fibril-forming ability (sometimes referred to as PTFE): Polytetrafluoroethylene, manufactured by Daikin Industries, Ltd., trade name: Polyfuron F201L. (14) Potassium diphenyl sulfone-3-sulfonate (sometimes referred to as KSS): SEAL SADN
Made by S CHEMICAL, trade name KSS.

[0029]

【Example】

[Examples 1 to 5] After mixing the components shown in Table 1 at the mixing ratios shown in Table 1, the cylinder temperature was measured using a 40 mmφ single screw extruder (manufactured by Isuzu Machine Co., Ltd.). 280 ° C
And pelletized. After drying the obtained resin composition pellets at 120 ° C. for 6 hours, using an injection molding machine (trade name: J-50EP, manufactured by Japan Steel Works, Ltd.), the cylinder temperature is 300 ° C. and the mold temperature is 80 ° C. A test piece was formed by using the method described above, and physical properties were evaluated. The results are shown in Table 1.

[Comparative Examples 1 to 6] The components shown in Table 2 were mixed at the compounding ratio shown in Table 2, and then mixed at 40 mmφ.
Using a single screw extruder (manufactured by Isuzu Processing Machine Co., Ltd.), pelletization was performed at a cylinder temperature of 280 ° C. After drying the obtained resin composition pellets at 120 ° C. for 6 hours, an injection molding machine (trade name: J-5, manufactured by Japan Steel Works, Ltd.)
0EP), cylinder temperature 300 ° C, mold temperature 8
Test specimens were molded at 0 ° C. and physical properties were evaluated. Table-Results
It is shown in FIG.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

Industrial Applicability The polycarbonate resin composition of the present invention has excellent flame retardancy and heat resistance, and also has an excellent balance between rigidity and impact resistance. It is very useful as a product, an OA device, for example, a housing or cover for a mobile terminal device, or a material for various components.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 27:18)

Claims (3)

[Claims] 1. A composition comprising (A) a polycarbonate resin of 95 to 50% by weight and (B) a glass fiber of 5 to 50% by weight, and (C) a phosphate compound of 0.5 to 10 parts by weight per 100 parts by weight of the polycarbonate resin. Parts by weight, (D) trihydrocarbyl (iso) cyanurate, (iso) cyanuric acid or an alkali metal salt of (iso) cyanuric acid 0.1 to 5
1. A polycarbonate resin composition, which is prepared by blending 0 to 2 parts by weight of polytetrafluoroethylene having a fibril-forming ability with (E). 2. The polycarbonate resin composition according to claim 1, wherein the (C) phosphate compound is a phosphate compound represented by the following general formula (1). Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, except when R ¹ , R ² , R ³ and R ⁴ are H, Represents a divalent or higher valent organic group;
Is 0 or 1, q is an integer of 1 or more, and r is 0
Where r is 0, at least one of R ¹ , R ³ and R ⁴ represents an organic group. ) 3. The glass fiber (B) is a chopped strand having a length of 1 to 6 mm and a diameter of 6 to 20 μm or a length of 0.1 to 6 μm.
The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition is a milled fiber having a diameter of 01 to 0.5 mm and a diameter of 6 to 20 μm.