JP5480071B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition.

Conventionally, a polycarbonate resin (hereinafter also referred to as “PC”) and a polymer alloy (hereinafter also referred to as “PC / PS alloy”) of this and a styrene resin have been used in various electric / electronic products and vehicle-related. Used in products.
For example, flat-screen TV housings, copiers, printers, facsimiles, personal computers, notebook-type or portable computer housings, chassis and other parts for office equipment, mobile phones, modems, media converters, and other communication equipment housings and parts, It is widely used in housings and parts for game machines, housings and parts for audio equipment, automobile headlamps and in-vehicle audio-related parts.
In recent years, environmental measures tend to be emphasized in the above-described applications, and demands for miniaturization, weight reduction, and high dimensionality of products are increasing. Based on these requirements, research has been conducted on techniques for improving high flame retardancy, high rigidity, and dimensional stability as well as thin-wall formability and precision formability.

In recent years, in Southeast Asia, the production and use of devices and parts in the various applications described above, and the use of outdoor devices such as solar cells are increasing.
In such an area, the resistance of the product resin in an environment of high temperature and high humidity is important, but at present, deterioration of physical properties due to lack of sufficient moisture resistance is often a problem.
In general, PC and PC / PS alloys are not highly moisture-resistant materials, and are particularly high even when a flame retardant is added and a resin composition reinforced with a reinforcing agent is used. The level of moisture resistance is not obtained.

  As a technique for improving the moisture resistance of a PC-based resin, a technique for suppressing residual components during polymerization of PC (see, for example, Patent Document 1), an acid value, impurities and moisture of a specific organophosphorus compound as a flame retardant Technology for controlling (for example, see Patent Documents 2 and 3), and technology for defining an acid value of a specific organophosphorus compound as a flame retardant in a material filled with a reinforcing agent (for example, see Patent Document 4). Is disclosed.

JP 2002-348459 A Japanese Patent Laid-Open No. 11-310695 JP 2004-217784 A JP 2000-191896 A

As described above, the use of PC resin and PC / PS alloys expands, and with the reduction in weight, thickness, and precision of parts using such materials, it has higher rigidity, higher dimensionality, and flame resistance. Excellent materials are being demanded.
However, the polycarbonate resin still has a point to be improved in terms of moisture resistance, and practically sufficient moisture resistance is not obtained particularly in a resin composition containing a flame retardant and a filler.
Insufficient moisture resistance adversely affects electrical properties, mechanical properties, and heat resistance, and therefore development of a resin composition having excellent moisture resistance is desired.

  In addition, if a large amount of filler is blended, the molding fluidity of the resin composition will decrease, so if the molded product becomes thinner, it will be necessary to perform injection molding at high temperatures, high speeds, and high pressures. Contamination and releasability of the mold surface due to additives and resin decomposition products become problems.

  Therefore, in the present invention, an object of the present invention is to provide a resin composition that improves mold release and mold contamination during injection molding, has excellent moisture resistance and good flame retardancy, and has excellent mechanical properties. And

As a result of various studies to solve the above problems, the present inventors have solved the above problems by controlling the content of each component and using a phosphorus compound having a predetermined structure as a flame retardant. As a result, the present invention has been completed.
That is, the present invention is as follows.

[1]
In the total of 100% by mass of the following (A), (B), (C) and (D),
(A) Polycarbonate resin 20-89 mass%,
(B) Styrenic resin 0-30% by mass,
(C) Phosphorus compound having an acid value of 1 or less represented by the following general formula (I): 1 to 30% by mass
as well as,
(D) Inorganic filler 10-60 mass%
A resin composition containing

In general formula (I), each A is independently selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or 6 to 20 carbon atoms. Represents any one selected from the group consisting of an aryl group and an aralkyl group having 7 to 12 carbon atoms, x and y are each independently an integer of 0 to 4, and n is each independently 0 or 1 and N is 1 to 30.

[2]
The resin composition according to [1], wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 50/50 to 100/0.
[3]
The resin composition according to [1] or [2], wherein the (C) phosphorus compound has an acid value of 0.5 or less.
[4]
The resin composition according to any one of [1] to [3], wherein the (C) phosphorus compound is a phosphorus compound represented by the following general formula (II).

  In general formula (II), N is 1-10.

[5]
The resin composition according to any one of [1] to [4], wherein (B) the styrene resin is a copolymer containing at least styrene and acrylonitrile as monomers.

  ADVANTAGE OF THE INVENTION According to this invention, the mold release property at the time of injection molding and mold contamination are improved, the resin composition which has the outstanding moisture resistance and favorable flame retardance, and was excellent also in the mechanical characteristic.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

(Resin composition)
The resin composition of the present embodiment is
In the total of 100% by mass of the following (A), (B), (C) and (D),
(A) Polycarbonate resin 20-89 mass%,
(B) Styrenic resin 0-30% by mass,
(C) Phosphorus compound having an acid value of 1 or less represented by the following general formula (I): 1 to 30% by mass
as well as,
(D) Inorganic filler 10-60 mass%
Is a resin composition containing

In general formula (I), each A is independently selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or 6 to 20 carbon atoms. Represents any one selected from the group consisting of an aryl group and an aralkyl group having 7 to 12 carbon atoms, x and y are each independently an integer of 0 to 4, and n is each independently 0 or 1 and N is 1-30.

Hereinafter, each component of the resin composition will be described in detail.
((A) Polycarbonate resin)
The polycarbonate (A) contained in the resin composition of the present embodiment (hereinafter sometimes abbreviated as “PC” or simply as “component (A)”) is a repeating unit represented by the following formula (1). It has a main chain consisting of
-(O-Ar-O-CO)-... Formula (1)
(In the formula (1), Ar is a divalent aromatic residue, and examples thereof include phenylene, naphthylene, biphenylene, pyridylene, and groups represented by the following formula (2).)
-Ar ^{1 -Y-Ar} 2 - ··· formula (2)
(In the formula (2), Ar ¹ and Ar ² are each independently an arylene group, for example, a group such as phenylene, naphthylene, biphenylene, pyridylene, etc. Y is an alkylene group or a substituted alkylene group. )
Moreover, (A) polycarbonate also includes the case where the bivalent aromatic residue shown by following formula (3) is contained as a copolymer component.
-Ar ^{1 -Z-Ar} 2 - ··· (3)
(In the formula (3), Ar ¹ and Ar ² are the same as Ar ¹ and Ar ² in the formula (2).
Z is a simple bond or a divalent group such as —O—, —CO—, —S—, —SO ₂ —, —CO ₂ —, —CONR ¹ —. R ¹ is independently selected from the group consisting of a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and an aryl group having 6 to 30 carbon atoms. It is. )
Specific examples of the divalent aromatic residue (Ar in the formula (1)) include those represented by the following formula (4).

In each chemical formula represented by the formula (4), R ⁷ and R ⁸ are each independently hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or 5 to 5 carbon atoms. It is any one selected from the group consisting of 10 cycloalkyl groups and aryl groups having 6 to 30 carbon atoms.
m and n are integers of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different. When n is 2 to 4, each R ⁸ is Each may be the same or different.

  Among the divalent aromatic residues represented by each chemical formula represented by the formula (4), a group represented by the following formula (5) is preferable.

  In particular, as the formula (1), a polycarbonate containing 85 mol% or more (based on all monomer units in the polycarbonate) of a repeating unit having the group represented by the formula (5) as Ar is particularly preferable.

  The polycarbonate (A) may contain a trivalent or higher aromatic residue as a copolymerization component.

  (A) The molecular structure of the polycarbonate terminal is not particularly limited, but preferably has one or more terminal groups selected from a phenolic hydroxyl group, an aryl carbonate group, and an alkyl carbonate group. Among these, a phenolic hydroxyl group, a phenyl carbonate group, a pt-butylphenyl carbonate group, p-cumylphenyl carbonate, and the like are more preferable as the terminal structure.

(A) When the molecular structure of the terminal of the polycarbonate has a phenolic hydroxyl group, the ratio of the phenolic hydroxyl terminal to the total number of terminal groups is not particularly limited, but from the viewpoint of obtaining better color tone and mechanical properties. The proportion of phenolic hydroxyl groups is preferably 20% or more of the total number of terminal groups, and more preferably in the range of 20 to 80%.
When the proportion of phenolic hydroxyl groups exceeds 80% of the total number of terminal groups, the thermal stability during melting of the resin composition tends to be slightly lowered.
The ratio of phenolic hydroxyl terminal is generally measured using NMR (NMR method), measured using titanium (titanium method), or measured using UV or IR (UV method or IR method). ).

(A) The weight average molecular weight (Mw) of the polycarbonate is generally 5,000 or more from the viewpoint of impact resistance, and preferably 200,000 or less, more preferably 10 from the viewpoint of the melt fluidity of the resin composition. 15,000 to 60,000, more preferably 15,000 to 40,000, and even more preferably 18,000 to 30,000.
The weight average molecular weight (Mw) is measured using gel permeation chromatography (GPC), and the measurement conditions are as follows.
That is, it is obtained by using a converted molecular weight calibration curve according to the following formula from the composition curve of standard monodisperse polystyrene using tetrahydrofuran as a solvent and polystyrene gel.
M _PC = 0.3591 M _PS ^1.0388
(In the above formula, _MPC is the weight average molecular weight of polycarbonate, and _MPS is the weight average molecular weight of polystyrene.)

(A) Polycarbonate can be produced by a known method. For example, it can be produced by a known method in which an aromatic dihydroxy compound and a carbonate precursor are reacted.
Specifically, an interfacial polymerization method (for example, phosgene method) in which an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) are reacted in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent, an aromatic dihydroxy compound and a carbonic acid diester (for example, A method of solid-phase polymerization of a crystallized carbonate prepolymer obtained by a transesterification method (melting method), a phosgene method or a melting method in which diphenyl carbonate) is reacted [Japanese Patent Laid-Open No. 1-158033 (US Pat. No. 4,948) , 871), JP-A-1-271426, and JP-A-3-68627 (corresponding to US Pat. No. 5,204,377)] and the like.

(A) As a preferable example of a polycarbonate, the polycarbonate resin which does not contain a chlorine atom manufactured by the transesterification method from dihydric phenol (aromatic dihydroxy compound) and carbonic acid diester is mentioned. A specific example is Wonderlight (trade name) manufactured by Asahi Kasei Co., Ltd.
In the present embodiment, as the polycarbonate resin (A), two or more kinds of polycarbonates having different structures and molecular weights can be used in combination.

((B) Styrenic resin)
The (B) styrenic resin (hereinafter sometimes simply referred to as component (B)) contained in the resin composition of the present embodiment is a styrenic compound in the presence or absence of a rubbery polymer. Or a polymer obtained by polymerizing a styrene compound and a compound copolymerizable with the styrene compound.
Examples of the styrene compound include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Is preferred.
The compound copolymerizable with the styrenic compound is not limited to the following. For example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, acrylic acid esters such as ethyl acrylate and butyl acrylate; methyl methacrylate and ethyl methacrylate And methacrylic acid esters such as butyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and maleic acid derivatives such as maleic anhydride and phenylmaleimide. In particular, acrylonitrile, methyl methacrylate, and butyl acrylate are preferable, and acrylonitrile is more preferable. These compounds are used together with the styrenic compound as described above. The proportion of the compound copolymerizable with the styrenic compound is preferably 60% by mass or less, more preferably 1 to 50% by mass, further preferably 5 when the total amount with the styrene compound is 100% by mass. It is -40 mass%, More preferably, it is 8-35 mass%.

  Examples of the rubbery polymer include, but are not limited to, conjugated diene rubbers, copolymers of conjugated diene compounds and aromatic vinyl compounds, ethylene-propylene copolymers, conjugated diene compounds and acrylate compounds. And a copolymer of ethylene and an acrylate compound, a rubber-like acrylate polymer, a chlorinated polyethylene, and the like. In particular, polybutadiene, styrene-butadiene random copolymer and styrene-butadiene block copolymer, and rubber components obtained by partially or substantially completely hydrogenating them may be mentioned, but the invention is not limited thereto.

Examples of commercially available (B) styrenic resins include (homo) polystyrene (atactic polystyrene), syndiotactic polystyrene, high impact polystyrene (rubber modified polystyrene), styrene-acrylonitrile copolymer, styrene-methyl methacrylate. Copolymer, rubber-modified styrene-acrylonitrile copolymer such as ABS resin and ACS resin, rubber-modified styrene-methyl methacrylate copolymer such as MBS resin and MABS resin, styrene- (meth) acrylate copolymer, styrene-anhydrous Examples thereof include maleic acid copolymers and styrene-maleimide copolymers.
Preferred (B) styrene resins include polystyrene (GPPS), rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS), rubber-modified styrene-acrylonitrile copolymer (ABS, AAS, AES, ACS), Examples thereof include rubber-modified styrene-methyl methacrylate copolymer (MBS) and rubber-modified styrene-acrylonitrile-methyl methacrylate copolymer (MABS). More preferable (B) styrene-based resin includes styrene-acrylonitrile copolymer (AS), polybutadiene-modified styrene-acrylonitrile copolymer (ABS), and polybutadiene-modified polystyrene (HIPS).
Various (B) styrenic resin mentioned above may be used individually by 1 type, and may use 2 or more types together.

(B) The method for producing the styrene-based resin is not particularly limited, and usual known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used. In particular, bulk polymerization, solution polymerization, and bulk suspension polymerization methods with few impurities such as alkali metals and metal compounds are preferably used, and bulk polymerization or solution polymerization is more preferable.
The (B) styrene resin may be a blend of different resins copolymerized separately.

(B) The content of the alkali metal used as a polymerization initiator or emulsifier during polymerization in the styrene resin is preferably as low as possible, preferably 1 ppm by mass or less, more preferably 0.5 ppm by mass or less, and even more preferably. It is 0.1 mass ppm or less.
Further, among the alkali metals, the content in the (B) styrene resin of the components of sodium and potassium is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, More preferably, it is 0.1 mass ppm or less.
(B) The alkali metal content in the styrene resin can be analyzed and measured by, for example, an ICP (high frequency induction plasma) method or an atomic absorption method.

((C) phosphorus compound)
The (C) phosphorus compound (hereinafter also referred to as component (C)) contained in the resin composition of the present embodiment is a phosphate ester compound represented by the following general formula (I).

In the general formula (I), each A is independently selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. R ¹ , R ² , R ³ and R ⁴ each independently represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or 6 carbon atoms. Represents any one selected from the group consisting of -20 aryl groups and aralkyl groups having 7 to 12 carbon atoms, x and y are each independently an integer of 0 to 4, and n is Each is independently 0 or 1, and N is 1-30.

In the general formula (I), each A is preferably independently a methyl group or a phenyl group, and more preferably a methyl group. R ¹ , R ² , R ³ and R ⁴ are each independently preferably an aryl group having 6 to 20 carbon atoms, and any one selected from the group consisting of a phenyl group, a xylenyl group and a cresyl group More preferably. x and y are each independently preferably 0 or 1, and more preferably 0. n is preferably 1. N is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.

  The phosphorus compound represented by the general formula (I) is generally a mixture of N different phosphorus compounds. In this case, N is expressed as an average value, and the average value may be within the above range. Therefore, it is not excluded that a phosphorus compound in which N is outside the above numerical range is included as an impurity. When N = 0, it represents a monophosphorus compound and is generally contained as an impurity.

  (C) The phosphorus compound is preferably a phosphorus compound represented by the following general formula (II) or the following formula (II) ′.

  In the general formula (II) or the general formula (II) ′, N is 1 to 30, preferably 1 to 10, and more preferably 1 to 5.

  The phosphorus compound represented by the general formula (II) or the general formula (II) 'is generally a mixture of N different phosphorus compounds. In this case, N is expressed as an average value, and the average value may be within the above numerical range. Therefore, it is not excluded that a phosphorus compound in which N is outside the above numerical range is included as an impurity. When N = 0, it represents a monophosphorus compound and is generally contained as an impurity.

The phosphorus compound (C) described above can be produced by the methods described in International Publication No. 2003/088942 and Japanese Patent Application Laid-Open No. 2008-202009. (C) A commercially available phosphorus compound may be used, for example, trade name: FP800 manufactured by ADEKA Corporation.
The (C) phosphorus compounds described above may be used alone or in combination of two or more.

The phosphorus compound (C) has an acid value of 1 or less, preferably 0.5 or less, and more preferably 0.1 or less.
When the acid value of the (C) phosphorus compound is within the above range, mold contamination is suppressed in the resin composition of the present embodiment, and characteristics such as moisture resistance tend to be good. The acid value is a value obtained according to JIS K2501, and is expressed as mg-KOH / g.

The crude product of the phosphorus compound (C) usually has a high acid value due to the influence of impurities. The acid value of the phosphorus compound (C) can be lowered by dissolving the phosphorus compound in toluene and washing with an aqueous solution containing an acid or a base, and the acid value can be controlled by the degree of washing.
(C) The measuring method of the acid value of a phosphorus compound is shown below. The following measurement method is an example, and as a method for specifying the acid value of the phosphorus compound (C) constituting the resin composition of the present embodiment, numerical values and specific materials included in the following measurement method It is not limited to.
Reagents used;
1) Solvent A mixed solution of 500 mL of toluene, 5 mL of distilled water and 495 mL of isopropyl alcohol.
2) Titration solution Commercially available 1 / 10N potassium hydroxide in isopropyl alcohol.
3) Indicator: 2 g of α-naphtholbenzein dissolved in 200 mL of the above solvent.
operation;
In a 300 mL Erlenmeyer flask, 50 g of the sample is precisely weighed, and 100 mL of the solvent is added to dissolve the sample. 3 mL of the indicator is added to the lysate, and immediately determined using the titrant. The orange color changes from green to greenish brown as the end point approaches. The determination of the end point is confirmed by the fact that the color remains changed for 15 seconds.
a formula;
Acid value (mgKOH / g) = [(A−B) × N × 56.1] / S
A: Amount of titrant required for sample titration (mL)
B: Amount of titrant required for titration in blank test (mL)
N: Normality of titrant (0.1)
S: Sample (g)

In the resin composition of the present embodiment, the above-described (C) phosphorus compound acts as a flame retardant. In the resin composition of the present embodiment, a known flame retardant may be used together with the component (C).
Examples of known flame retardants include phosphate ester compounds other than component (C), phosphazene compounds, phosphinic acid metal salt compounds, polyphosphates, red phosphorus, and the like. One or more known flame retardants selected from these can be used in combination with the above-described component (C) in the range of 50% by mass or less of the total amount of the flame retardants.

((D) inorganic filler)
Examples of the (D) inorganic filler (hereinafter sometimes referred to as component (D)) contained in the resin composition of the present embodiment include glass fiber, carbon fiber, potassium titanate fiber, and plate shape. Or natural minerals such as glass flakes, glass flakes (Nippon Sheet Glass registered trademark), glass beads, mica, talc, chlorite, wollastonite, kaolinite, calcined clay, calcium carbonate, heavy calcium carbonate, shirasu balloon, etc. Artificial fillers may be mentioned.
These components (D) may be used individually by 1 type, and may be used together 2 or more types.

In addition, the shape of the (D) inorganic filler may be any of a fibrous shape, a plate shape (including a scale shape and a layer shape), a needle shape, and a spherical shape.
The (D) inorganic filler preferably contains a plate-like filler from the viewpoint of dimensional characteristics of the molded product (warp, directional direction of dimensions, etc.).
Many patent documents disclose that a resin composition containing a plate-like filler is excellent in dimensional characteristics. For example, WO 95/27603, JP 62-109855, JP 06-157896, JP 06-172635, JP 08-183902, and JP 09-7208. Gazette, JP-A 09-12733, JP-A 2002-352542, JP-A 2003-41131, JP-A 2004-315645, JP-A 2004-323565, JP-A 2005-320473, etc. The plate-like (scale-like and layer-like) inorganic filler described in these prior arts is included in (D) the inorganic filler contained in the resin composition of the present embodiment.

The component (D) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, based on the total amount of the component (D). More preferably, it contains 50 mass% or more.
(D) By including at least one plate-like filler as the inorganic filler in the above blending amount, excellent dimensional characteristics can be obtained.

(D) As the inorganic filler, mica is preferably used from the viewpoint of the balance between the strength and dimensional characteristics of the resin composition of the present embodiment, and chlorite is preferably used in terms of flame retardancy.
(D) The glass fiber as the inorganic filler preferably has an average diameter of 20 μm or less from the viewpoint of improving the mechanical strength of the resin composition of the present embodiment and reducing the warpage of the molded product. The thing of 5-15 micrometers is more preferable from a viewpoint of the balance of a mechanical characteristic and a dimensional characteristic. The fiber length of the glass fiber is not particularly limited, and uncut glass roving can also be used. In addition, a chopped strand of about 3 to 15 mm is generally commercially available and is preferable from the viewpoint of handling. When the chop strands are used, the number of bundling is preferably 100 to 5000. The composition of the raw material glass in the case of producing glass fibers is preferably non-alkali, and examples thereof include E glass.

(D) As an inorganic filler, from the viewpoint of the dimensional characteristics of the resin composition of the present embodiment, glass fibers having a fiber length of about 0.1 to 0.5 mm, which are commercially available as cut fibers, and commercially available as milled fibers. It is preferable to use powdered glass fibers having a fiber length of 0.1 mm or less.
When emphasizing the strength of the resin composition of the present embodiment, it is preferable to use glass roving long fibers and chopped strands, and when emphasizing appearance and dimensional anisotropy, cut fibers and milled fibers are preferably used.
These various glass fibers are available from many glass manufacturers.
As the type of glass, E glass is generally used, but C glass and ECR glass can also be used.

Although the various glass fibers described above can be used as they are, it is generally preferable to use them after treating them with a surface treatment agent and a sizing agent for improving the adhesion to the resin.
The sizing agent is usually composed of a film forming agent, a surfactant, a softening agent, an antistatic agent, a lubricant and the like.
As the surface treatment agent, various coupling agents may be used for the purpose of enhancing the affinity between the resin component and the glass fiber or the interfacial bond strength (adhesion).
As the coupling agent, coupling agents such as silane, chrome, and titanium can be used. In particular, epoxy silane such as γ-glycidoxypropyltrimethoxysilane; vinyltrichlorosilane; γ-aminopropyltri Those containing a silane coupling agent such as aminosilane such as ethoxysilane are preferred.
When treating with surface treatment agents and sizing agents, treatment with various surfactants such as nonionic, cation, and anionic types, and dispersants such as fatty acids, metal soaps, and various resins can be performed together. This is preferable from the viewpoint of improving the mechanical strength and kneadability of the resin composition of the embodiment.

  (D) Carbon fiber as an inorganic filler is a commercial product such as Torayca (registered trademark) cut fiber or milled fiber manufactured by Toray Industries, Inc., Pyrofil (registered trademark) chopped fiber manufactured by Mitsubishi Rayon Co., Ltd. Can be used.

  (D) As a potassium titanate fiber as an inorganic filler, Tismo (registered trademark) manufactured by Otsuka Chemical Co., Ltd. can be used as a commercial product.

When the dimensional anisotropy of the molded product is particularly important, the resin composition of the present embodiment preferably contains a plate-like or scale-like (D) inorganic filler as the component (D). As the plate-like or scale-like inorganic filler, plate-like or scale-like glass, mica, chlorite and talc are preferable.
As a method for producing plate-like or scale-like glass, a balloon method for crushing a balloon made of molten glass, a span method using ultracentrifugal force, or the like is known. Generally, those having a weight average diameter by sieving of 0.05 mm to 2 mm and a thickness of 1 to 10 μm are used, and the major axis in the resin composition of the present embodiment is 1000 μm or less, preferably in the range of 1 to 500 μm, and weight. An average aspect ratio (ratio of weight average major axis to weight average thickness) is 5 or more, preferably 10 or more, more preferably 30 or more.
When preparing a resin composition by mixing plate-like or scale-like glass with other components, the plate-like or scale-like glass is destroyed and its size is reduced. Measurement of the long diameter and thickness of plate-like or scale-like glass in the resin composition is performed by dissolving the resin composition, filtering and taking out the plate-like or scale-like glass, and observing with an optical microscope or a scanning electron microscope. Can be done.
When the plate-like or scale-like glass is longer than 2 mm, uniform mixing with the resin becomes difficult during blending with the resin, and the physical properties of the molded product may be uneven. On the other hand, when the aspect ratio is less than 5, the effect of improving the heat distortion temperature of the molded article cannot be sufficiently obtained, and the Izod impact strength and rigidity tend to decrease.

  The plate-like or scale-like glass is preferably treated with a surface treatment agent and a sizing agent, like the glass fiber described above. For the purpose of improving the affinity with the resin, for example, a silane-based (for example, aminosilane-based glass) ) And titanate-based various surface-treating agents can be used.

  Examples of commercial products of plate-like or scale-like glass include Nihon-Plate Glass Co., Ltd.'s Micro Glass Fleka (registered trademark), and GLASS FLAKE Limited (UK), scale-like glass. Although what is marketed as plate-like or scale-like glass can be used as it is, you may use it, after grind | pulverizing appropriately, before mix | blending with resin.

(D) Mica as an inorganic filler is a scale-like aluminum silicate-based mineral, for example, KAl ₂ (AlSi ₃ O ₁₀ ) (OH) ₂ (white mica), K (Mg, Fe) ₃ (AlSi ₃ O ₁₀ ) (OH) ₂ (black mica), KMg ₃ (AlSi ₃ O ₁₀ ) (OH) ₂ (gold mica), KLi ₂ Al (Si ₄ O ₁₀ ) (OH) ₂ (scale mica), NaAl ₂ Examples include various mica represented by chemical formulas of (AlSi ₃ O ₁₀ ) (OH) ₂ (soda mica) and KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ (fluorine gold mica).
These mica have cleavage properties, and any mica can be used in this embodiment.
The average particle diameter of mica is preferably from 3 to 200 μm (sieving method), more preferably from 5 to 150 μm, from the viewpoint of achieving a good balance between the rigidity and dimensional characteristics of the resin composition of the present embodiment. Preferably it is 10-100 micrometers. When the average particle size is 3 μm or more, the effect on the reinforcing effect and dimensionality is remarkable, and when the average particle size is 200 μm or less, the decrease in weld strength and the deterioration of the surface appearance of the molded product are small.

(D) Talc as an inorganic filler is generally one in which the main component is magnesium silicate and contains impurities such as calcium, iron, sodium and potassium as impurities.
The talc used in this embodiment is preferably a pulverized and classified natural talc, and more preferably a flaky or flat mineral.
The talc preferably has a chemical composition represented by 4SiO ₂ .3MgO.H ₂ O as hydrous magnesium silicate. The hydrous magnesium silicate is usually composed of 55 to 63% by mass of SiO ₂ , 25 to 33% by mass of MgO, and about 5% by mass of loss on ignition (H ₂ O), depending on the production area. Other minor components include 0.1 to 5% by mass of Fe ₂ O ₃ , 0.1 to 3% by mass of Al ₂ O ₃ , 0.1 to 5% by mass of CaO, and the like.

The average particle size of the talc is not particularly limited, but is usually preferably 0.5 μm to 20 μm (sieving method), more preferably 1 μm to 15 μm, still more preferably 1.5 μm to 10 μm. .
When the average particle size of the talc is 0.5 μm or more, the effect on the reinforcing effect and the dimensional property is remarkable, and when the average particle size of the talc is 20 μm or less, the weld strength of the molded product is reduced. The deterioration of the surface appearance tends to be small.

(D) The chlorite as the inorganic filler is preferably a chlorite group natural ore.
Chlorite group ore is an oxide made of Mg, Fe, Mn, Ni, etc., an oxide made of Al, Fe, Cr, Ti, etc., or a predetermined oxide selected from each group of oxides made of Si, Al, etc. This is an ore containing materials, and there are monoclinic and orthorhombic crystal structures.
The average particle size of the chlorite group ore is not particularly limited, but is preferably 0.5 μm to 30 μm (sieving method), more preferably 1 μm to 20 μm, and still more preferably 3 μm to 15 μm.
When the average particle size of the chlorite group ore is 0.5 μm or more, the effect on the reinforcing effect and dimensionality is remarkable, and when the average particle size of the chlorite group ore is 30 μm or less, a molded product There is a tendency that a decrease in weld strength and a deterioration in surface appearance are reduced.
In the resin composition according to the present embodiment, it is considered that the inclusion of chlorite group ore not only improves the mechanical properties and dimensional characteristics but also exhibits a flame retardant effect.
Chlorite group minerals include chlorite, cookite, and nanthite. These may be used alone or in combination of two or more. In particular, chlorite is preferable from the viewpoint of availability. As the chlorite product, products manufactured by Fuji Talc Industry Co., Ltd. or Sakai Industry Co., Ltd. can be used.

(D) Wollastonite as an inorganic filler is preferably white needle-like crystalline mineral which is expressed by CaO · SiO ₂ and is naturally produced, and may be synthesized.
The wollastonite has a fiber shape to a lump shape, and the fiber shape is preferably used.
Further, since wollastonite having a large fiber diameter is easily broken during melt-kneading, it is preferable to use wollastonite containing a component having a fiber diameter of 5 μm or less in an amount of 80% by mass or more, preferably 95% by mass or more.
The average fiber diameter of wollastonite in the previous stage (initial stage) of the production of the resin composition is preferably 2 to 30 μm, more preferably 3 to 20 μm, still more preferably 4 to 15 μm.
If the average fiber diameter is less than 2 μm, the resin composition tends to break during processing, and if it exceeds 30 μm, the reinforcing effect is small. The initial average fiber length of wollastonite is preferably 20 to 400 μm, more preferably 25 to 300 μm, and still more preferably 30 to 250 μm.
If the average fiber length is less than 20 μm, the reinforcing effect of the resin composition is small, and if it exceeds 400 μm, it tends to break during processing.
Further, the wollastonite preferably has an initial average fiber length divided by an initial average fiber diameter (= initial average aspect ratio) of 4 to 50, more preferably 5 to 40, still more preferably. Is 6-30. When the average aspect ratio is 4 or more, a sufficient reinforcing effect is obtained, and when it is 50 or less, breakage in the production process of the resin composition can be prevented.

  In the resin composition of the present embodiment, particularly when a plate-like filler (including scale-like or layered filler) is used, the flame retardant aromatic condensed phosphate ester compound that has been suitably used in the past is used. When combined, smoke suppression and mold contamination during injection molding are improved, and the balance between heat resistance and fluidity, impact resistance, flame retardancy, and moisture absorption properties tend to be excellent. The resin composition having the above characteristics is extremely useful for various thin parts, precision parts and the like that require strict dimensional characteristics.

(Composition ratio of component (A) to component (D))
The resin composition of the present embodiment includes (A) polycarbonate resin: 20 to 89% by mass, (B) styrene resin: 0 to 30% by mass, and (C) a specific phosphorus compound having an acid value of 1 or less: 1 -30 mass% and (D) inorganic filler: 10-60 mass% is contained.
In the resin composition of this embodiment, the ratio of each component varies depending on the use of the resin composition, and a desired composition is selected within the above range depending on the required level of heat resistance, mechanical properties, dimensionality, flame retardancy, etc. Is done.

  In the resin composition of the present embodiment, the total content of the (A) polycarbonate resin and the (B) styrene resin is a required characteristic depending on the ratio of the (A) polycarbonate resin and (B) styrene resin described later. Although it is arbitrarily selected according to, it is preferable that it is 20-90 mass%, More preferably, it is 20-80 mass%, More preferably, it is 30-70 mass%.

Here, the mass ratio ((A) / (B)) of the (A) polycarbonate resin and the (B) styrene resin is preferably 50/50 to 100/0, more preferably 40/60 to 100/0. More preferably, it is in the range of 30/70 to 95/5, and a desired ratio can be selected from the viewpoint of balance between fluidity, heat resistance and flame retardancy.
In the resin composition according to the present embodiment, in such a composition range in which the ratio of the polycarbonate resin (A) is high, that is, in a composition range that requires high-temperature molding, mold contamination (MD or the like) particularly with respect to conventional materials. Inhibiting effect and water absorption properties are excellent.

  In the resin composition according to the present embodiment, the content of the (C) phosphorus compound is 1 to 30% by mass, preferably 3 to 25% by mass, and more preferably 5 to 20% by mass. The content of the (C) phosphorus compound is appropriately determined according to the required flame retardancy level and taking into account heat resistance, and taking into account the blending ratio of the (A) polycarbonate resin. %, The flame retardancy effect is exhibited, and when it is 30% by mass or less, the flame retardancy effect is sufficiently exhibited, and the heat resistance and mechanical properties can be maintained.

In the resin composition of the present embodiment, the content of the (D) inorganic filler is 10 to 60% by mass when the total of the components (A) to (D) described above is 100% by mass. The amount is preferably 20 to 60% by mass, more preferably 30 to 60% by mass, and still more preferably 40 to 50% by mass.
(D) The content of the inorganic filler is appropriately determined together with the type of the inorganic filler in consideration of the dimensional characteristics and mechanical characteristics, but the effect of improving the dimensional characteristics and strength is manifested at 10% by mass or more. Good moldability is obtained at a mass% or less, and mechanical properties and heat resistance are improved.
In particular, when the content of the inorganic filler (D) is 40% by mass or more, it is necessary to perform injection molding under high temperature, high speed, and high pressure conditions in the molding process of the resin composition. Even under molding conditions, the resin composition of the present embodiment is excellent in the effect of preventing mold contamination and exhibits excellent moisture resistance.

(Other ingredients)
<Flame retardant aid>
The resin composition according to the present embodiment may contain polytetrafluoroethylene, a phenol resin, a silicone resin, a cyclic nitrogen compound such as melon and melem, and the like as a flame retardant aid.
The content of the flame retardant aid is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.02 to 5 parts by mass with respect to 100 parts by mass in total of the components (A) to (D) described above. It is.
The polytetrafluoroethylene preferably has a molecular weight of 100,000 or more, more preferably about 200,000 to 3,000,000.
By adding polytetrafluoroethylene, dripping during combustion is suppressed.
Furthermore, when polytetrafluoroethylene and a silicone resin are used in combination, drip can be further suppressed and the combustion time can be shortened as compared with the case of polytetrafluoroethylene alone.
In addition, various conventionally known flame retardants and flame retardant aids, for example, hydroxides such as magnesium hydroxide and aluminum hydroxide, zinc borate compounds, zinc stannate compounds, silica, silica alumina, etc. By adding an inorganic silicon compound or the like, flame retardancy can be further improved.

<(E) Hydrogenated block copolymer, (F) polyolefin resin>
The resin composition according to the present embodiment has (E) a specific hydrogenated block copolymer (hereinafter, also referred to as component (E)) and the purpose of improving impact resistance, releasability and chemical resistance. It is preferable to add (/ F) polyolefin resin (hereinafter also referred to as component (F)).

(E) A hydrogenated block copolymer is a copolymer obtained by hydrogenating a block copolymer of styrene and a diene compound.
(E) The hydrogenated block copolymer has a styrene polymer block chain having a number average molecular weight of 15000 or more, and the block copolymer of styrene and a diene compound is hydrogenated to obtain the degree of unsaturation of the diene compound polymer block chain. It is preferable to have a structure in which is reduced to 20% or less.
The hydrogenated block copolymer of styrene and a diene compound can be produced by a generally known method. A styrene polymer block chain (hereinafter also referred to as “A”) and a diene compound polymer block chain (hereinafter referred to as “B”). A block copolymer obtained by hydrogenation of a block copolymer consisting of ABA, ABA, AB, (AB) ₄ -Si, A- A hydrogenated product of a styrene-diene compound block copolymer having a bond structure such as B-A-B-A is preferred.
Further, the microstructure of the diene compound polymer block chain can be arbitrarily selected, but in general, the 1,2-vinyl bond is preferably 2 to 60%, more preferably 8 to 40%.
Preferred diene compounds include butadiene and / or isoprene.
These hydrogenated block copolymers are commercially available, and examples thereof include Tuftec from Asahi Kasei Chemicals Corporation, Septon from Kuraray Co., Ltd., and Kraton from Kraton Polymer Co., Ltd.

In addition, as other hydrogenated block copolymers composed of styrene and a diene compound having a structure different from that of the above-mentioned hydrogenated block copolymer, a block of a random copolymer of styrene and a diene compound (hereinafter referred to as “C”). A random hydrogenated block copolymer containing the hydrogenated product of (2).
Examples of the structure include A-C, A-C-A, A-C-A-C, (A-C-) ₄ -Si, A-B-C, A-B-C-A, C- Examples thereof include hydrogenated products of styrene-diene compound block copolymers having various bond structures such as AC.
This random hydrogenated copolymer is commercially available, and examples thereof include SOE (registered trademark) manufactured by Asahi Kasei Chemicals Corporation.

  (E) The styrene polymer block chain of the hydrogenated block copolymer must have at least one block chain having a number average molecular weight of 15,000 or more, more preferably 20,000 or more, and even more preferably all styrene heavy chains. The number average molecular weight of the combined block chain is 15,000 or more.

(E) If the number average molecular weight of a styrene polymer block chain is 15,000 or more, the ratio of a styrene polymer block and a diene compound polymer block will be sufficient for a hydrogenated block copolymer from a viewpoint of easy mixing. However, the content of the styrene polymer block component is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.
When the number average molecular weight of the styrene polymer block chain is 15,000 or more, the combined use effect with the (F) polyolefin resin described later is achieved, and the resin composition is excellent in impact resistance while improving releasability. Is obtained.

  (F) Polyolefin resin is a homopolymer of olefinic hydrocarbons, a copolymer of ethylene and α-olefin, and a copolymer of ethylene and acrylates, such as low density polyethylene, Examples thereof include high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, and ethylene-butyl acrylate copolymer. Preferred (F) polyolefin resins are low density polyethylene and ethylene-propylene copolymers.

  (F) The polyolefin resin may be added alone without adding the (E) hydrogenated block copolymer if the purpose is to improve the releasability, in which case the component (A ), Component (B), component (C), and component (D), the total amount of component (F) is preferably 1 part by mass or less.

  As will be described later, the resin composition of the present embodiment uses (E) a specific hydrogenated block copolymer and (F) a polyolefin-based resin in a specific amount and a specific ratio, thereby providing rigidity and impact resistance. The effect of improving the property is obtained.

  In the resin composition of the present embodiment, (E) a hydrogenated block copolymer of styrene and a diene compound in which the number average molecular weight of the styrene polymer block chain is 15000 or more, and (F) a polyolefin resin are contained. Preferably, these addition amounts are preferably 0.1 to 7 parts by mass, more preferably 100 parts by mass for each of the total of component (A), component (B), component (C) and component (D). Are in the range of 0.3 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, respectively, and the total amount of component (E) and component (F) is 10 parts by mass or less, preferably 7 parts by mass. Part or less, more preferably 5 parts by weight or less.

  The total amount of the component (E) and the component (F) is preferably 5 parts by mass or less and more preferably 3 parts by mass or less from the viewpoint of the rigidity of the resin composition of the present embodiment.

The mass ratio ((E) / (F)) of (E) hydrogenated block copolymer and (F) polyolefin resin is preferably in the range of 90/10 to 10/90, more preferably 60. / 40 to 15/85, more preferably 55/45 to 25/75, and even more preferably 50/50 to 30/70.
When the mass ratio ((E) / (F)) between the component (E) and the component (F) is within the above range, the impact resistance improvement effect can be expected significantly.

<Synthetic resin>
If necessary, the resin composition of this embodiment may be melt-mixed with a synthetic resin other than the above-described components, which is conventionally known as a polymer alloy with a polycarbonate resin.
For example, polybutylene terephthalate, polyethylene terephthalate, polytetramethylene terephthalate, LCP, and other polyester resins; polyorganosiloxane rubber components and polyalkyl (meth) acrylate rubber components are intertwined alternately and combined and integrated. A composite rubber graft copolymer obtained by graft-polymerizing one or more vinyl monomers to a composite rubber (disclosed in JP-A Nos. 64-79257 and 7-207137) And the method disclosed in JP-A-7-207132).

<Additives>
The following other additives may be added to the resin composition of the present embodiment as necessary.
For example, a stabilizer such as an antioxidant (also referred to as a heat stabilizer), an ultraviolet absorber, or a light stabilizer can be added to improve the heat stability and light resistance of the resin composition.
Specific examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol and n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate. 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,4-bis [(octylthio) methyl] -0 -Cresol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- [1- Hindered such as (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl)] acrylate Enol antioxidants; sulfur antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate pentaerythritol-tetrakis (β-lauryl thiopropionate); tris (nonylphenyl) phosphite, tris ( 2,4-di-t-butylphenyl) phosphite and other phosphorus antioxidants, epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, Examples include epoxy stabilizers such as 4′-epoxycyclohexanecarboxylate, other alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and heterocyclic epoxy compounds. These may be used alone or in combination of two or more.

Specific examples of ultraviolet absorbers and light stabilizers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) benzo Benzotriazole ultraviolet absorbers such as triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, and benzophenones such as 2-hydroxy-4-methoxybenzophenone And ultraviolet light absorbers or hindered amine light stabilizers.
These may be used alone or in combination of two or more. Moreover, you may use together an ultraviolet absorber and a light stabilizer.

  The blending ratio of the various stabilizers described above is not particularly limited, but is generally 0.01 to 5 parts by mass with respect to 100 parts by mass in total of (A) polycarbonate resin and (B) styrene resin. More preferably, it is 0.02-3 mass parts, More preferably, it is the range of 0.03-1 mass parts.

<Fillers>
In addition to the inorganic filler (D) described above, various other fillers may be blended in the resin composition of the present embodiment.
Specific examples of other fillers include basic magnesium sulfate, seplite, zonotlite, aluminum borate, colloidal calcium carbonate, soft calcium carbonate, silica, titanium oxide, barium sulfate, zinc oxide, alumina, magnesium hydroxide, hydro Talsite, silica beads, alumina beads, carbon beads, glass balloons, metallic conductive fillers, nonmetallic conductive fillers, magnetic fillers, piezoelectric / pyroelectric fillers, slidable fillers, fillers for sealing materials, UV absorption Examples thereof include fillers, vibration damping fillers, ketjen black, and acetylene black.
These various fillers are selected according to the intended use of the resin composition.

<Other ingredients>
The resin composition of the present embodiment further includes rubber-like substances other than those described above, alicyclic saturated hydrocarbon resins, terpene resins, aliphatic petroleum resins, aromatic petroleum resins and various elastomers thereof, Modified products of resins, higher fatty acid esters, higher fatty acid metal salts, various waxes, petroleum hydrocarbons, polyoxyalkylenes, fluororesins, antistatic agents, various additives such as dyes and pigments as colorants It may be added, so that the material that is finally suitable for the intended use can be obtained.
The rubber-like substance is a polymer having a glass transition temperature of −100 ° C. or more and 50 ° C. or less, or a copolymer obtained by copolymerizing a monomer of the polymer, for example, isoprene-based, butadiene-based, olefin-based, Examples thereof include polyester elastomer-based and acrylic polymers or copolymers. Of these, general-purpose ones include butadiene and olefin.
Furthermore, a ternary copolymer with an acid component is also useful. Specifically, acrylic acid-butadiene-styrene copolymer, carboxylic acid / carboxylic anhydride-containing acid compound-butadiene-styrene copolymer, etc. Is mentioned. Further, similarly to the butadiene rubber-like substance, an olefin rubber component modified with an acid component is also useful, and an epoxy group-containing olefin rubber component can also be used.
The alicyclic saturated hydrocarbon resin is a hydrogenated product of an aromatic hydrocarbon resin. Such aromatic hydrocarbon resins generally include C9 hydrocarbon resins, C5 / C9 hydrocarbon resins, indene-coumarone resins, vinyl aromatic resins, terpene-vinyl aromatic resins and the like. The higher the hydrogenation rate, the better and preferably 30% or more.
Examples of the rupene resins include terpenes made from α-pinene, β-pinene, and dipentenes. Those modified or hydrogenated with aromatic hydrocarbons (phenol, bisphenol A, etc.) can also be used.

The higher fatty acid esters, higher fatty acid metal salts, and waxes are effective as processing aids for improving fluidity and releasability.
As the wax, olefin wax, montan wax and the like are generally used, and in particular, low molecular weight polyethylene is excellent in versatility.

A liquid petroleum fraction is preferably used as the aliphatic petroleum resin.
As the aromatic petroleum resin, an aromatic hydrocarbon fraction polymer represented by C9 carbons is used.

The antistatic agent generally has the effect of exerting its effect by imparting hygroscopicity to the surface of the molded body.
The antistatic agent may be used as an additive in the resin or may be applied by secondary processing such as coating. Examples of the antistatic agent used as an additive include polyalkylene glycol, polyalkylene oxide, and polyalkyl sulfonate.

[Method for producing resin composition]
The resin composition of this embodiment can be manufactured by melt-mixing each component mentioned above on heating conditions.
As the melt mixer, an extruder, more preferably a twin screw extruder, more preferably a twin screw extruder capable of appropriately selecting a screw configuration including a kneading block can be used.
Furthermore, the raw material hopper and the raw material supply port can be supplied with an inert gas (for example, nitrogen) to bring the oxygen concentration of the extruder system to an atmosphere of 1% or less, and have at least one vent port and a vacuum. An apparatus having devolatilization capability, having a facility for applying an external lubricant such as a higher fatty acid metal salt after water-cooling and pelletizing the strand, a product hopper that does not absorb moisture, and a packaging facility are preferable.

In the step of melt-mixing each component using an extruder, all the components may be supplied from the first supply port and melt-mixed, but (A) polycarbonate resin, (B) styrenic resin, and ( C) It is preferable that the phosphorus compound is supplied from the first supply port and kneaded, and then (D) the inorganic filler is supplied and melt-mixed at the second supply port and thereafter.
Also, intermediate raw material pellets of a resin composition obtained by kneading (A) polycarbonate resin, (B) styrene resin and (C) phosphorus compound in the first extruder are produced, and the other second extruder Thus, a two-stage melt mixing extrusion method in which the intermediate raw material pellets, (D) inorganic filler, and further other additives are melt-kneaded is also suitable.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

<Component (A): Polycarbonate>
(A): PC (polycarbonate of bisphenol A)
(Trade name: Wonderlight PC-110, manufactured by Asahi Kasei Co., Ltd.)

<Component (B): Styrenic resin>
(B-1): AS resin (styrene-acrylonitrile copolymer resin)
(Trademark Stylac AS 789, manufactured by Asahi Kasei Chemicals Corporation)
(B-2): AS resin (styrene-acrylonitrile copolymer resin)
The manufacturing method of a styrene-acrylonitrile copolymer (B-2) is shown below.
A mixed liquid consisting of 4.7 parts by mass of acrylonitrile, 73.3 parts by mass of styrene, 22 parts by mass of ethylbenzene, and 0.02 parts by mass of t-butylperoxy-isopropyl carbonate as a polymerization initiator was added at 2.5 liters per hour. The polymer was continuously fed at a flow rate to a fully mixed reactor having a capacity of 5 liters, and polymerization was carried out at 142 ° C. until the polymerization rate reached 60% to obtain a polymerization solution.
The polymerization liquid is continuously led to an extruder with a vent, unreacted monomers and solvent are removed under conditions of 260 ° C. and 40 Torr, and the polymer is continuously cooled, solidified and chopped to form particulate styrene- An acrylonitrile copolymer (referred to as B-2) was obtained.
The composition of this styrene-acrylonitrile copolymer was analyzed by infrared absorption spectroscopy. As a result, it was 9% by mass of acrylonitrile units and 91% by mass of styrene units.
The melt flow rate was 90 g / 10 min (according to ASTM D-1238, measured at 220 ° C. and 10 kg load).
(B-3): ABS resin (acrylonitrile-butadiene-styrene copolymer resin)
(Nippon A & L Co., Ltd., trademark Santac UT-61)
(B-4): HIPS resin (high impact polystyrene)
(Manufactured by PS Japan, PSJ polystyrene H8117)

<Component (C): Phosphate ester compound>
(C-1): A phosphorus compound having N = 1 as the main component (about 85% in terms of area ratio according to liquid chromatography analysis) and an acid value of 0.1 or less in the following chemical formula (II).

(C-2): The same phosphorus compound as (C-1) except that the acid value is 0.3.
(C-3): The same phosphorus compound as (C-1) except that the acid value is 0.7.
(C-4): A phosphorus compound similar to (C-1) except that the acid value is 1.3.
(C-5): A phosphorus compound having the following chemical formula (II) ′ where N = 1 is the main component (about 85% in terms of area ratio by liquid chromatography analysis) and the acid value is 0.1 or less.
The acid value of the phosphorus compound was lowered by dissolving the phosphorus compound in toluene and washing with an aqueous solution containing an acid or base, and the acid value was controlled by the degree of washing.
(C) The measuring method of the acid value of a phosphorus compound is shown below.
Reagents used;
1) Solvent A mixed solution of 500 mL of toluene, 5 mL of distilled water and 495 mL of isopropyl alcohol.
2) Titration solution Commercially available 1 / 10N potassium hydroxide in isopropyl alcohol.
3) Indicator: 2 g of α-naphtholbenzein dissolved in 200 mL of the above solvent.
operation;
In a 300 mL Erlenmeyer flask, 50 g of the sample was precisely weighed, and 100 mL of the solvent was added to dissolve the sample. 3 mL of the indicator was added to the lysate, and immediately determined using the titrant. As the end point approaches, the orange color changed from green to greenish brown. The determination of the end point was confirmed by the fact that the color remained changing for 15 seconds.
a formula;
Acid value (mgKOH / g) = [(A−B) × N × 56.1] / S
A: Amount of titrant required for sample titration (mL)
B: Amount of titrant required for titration in blank test (mL)
N: Normality of titrant (0.1)
S: Sample (g)

  (C-6): As a phosphorus flame retardant, manufactured by Daihachi Chemical Industry Co., Ltd., product name CR741 (main component is bisphenol A aromatic condensed phosphate ester compound, acid value of 0.1 or less).

<Component (D): Inorganic filler>
(D-1) Glass fiber: manufactured by Nippon Electric Glass Co., Ltd., 13 μm / 3 mm chopped strand, product name T-511.
(D-2) Glass flake: Nippon Sheet Glass Co., Ltd., product name CEF150A.
(D-3) Gold mica: Product name Kuraray Co., Ltd., product name: Suzolite Mica 200KI.
(D-4) White mica: Product name Repcomica C-100IF, manufactured by Repco.
(D-5) Talc: manufactured by Takehara Chemical Co., Ltd., product name Hytron A.
(D-6) Chlorite: manufactured by Fuji Talc Kogyo Co., Ltd., product name WL-13M.

<Component (E): Hydrogenated block copolymer (SEBS)>
Asahi Kasei Chemicals Co., Ltd., product name Tuftec H1081, which is a hydrogenated styrene-butadiene block copolymer, was used.

<Component (F): Polyolefin resin>
(F-1): Low density polyethylene (LDPE), manufactured by Asahi Kasei Chemicals Corporation, product name Suntec LD-M2004.
(F-2): Ethylene-propylene copolymer (EP), manufactured by Mitsui Chemicals, Tuffmer P0680.

[Characteristic evaluation method, etc.]
Evaluation of the obtained resin composition was performed by the following methods and conditions.
<(1) Material characteristics>
Material properties were measured based on ISO standard physical property tests.
(Preparation of test piece)
The obtained resin composition pellets were dried at 100 ° C. for 4 hours, and then ISO-GN molding machine manufactured by Toshiba Machine Co., Ltd. (cylinder temperature set to 280 ° C. and mold temperature set to 70 ° C.) A test piece was molded according to 7391-2.
Charpy impact strength: Measured with a notch in accordance with ISO-179 using the above test piece.
Tensile strength: measured using the above test piece in accordance with ISO-527 at a test speed of 5 mm / min.
Flexural modulus: measured using the above test piece in accordance with ISO-178 at a test speed of 2 mm / min.

<(2) Moisture resistance test>
The moisture resistance was compared and evaluated by the following accelerated test.
Using a test piece for measuring the tensile strength of ISO-527, leaving the test piece for 500 hours in a thermo-hygrostat (layer) set at 90 ° C. and a relative humidity of 90%. (23 ° C., 50% relative humidity) for 24 hours.
Thereafter, the tensile strength (TS500) of the test piece was measured.
The tensile strength TS0 of the test piece under standard condition adjustment (23 ° C., relative humidity 50%, 24 hours or more) is measured in advance, and the tensile strength tensile with respect to the tensile strength (TS0) under standard condition adjustment is measured. The ratio of strength (TS500) TS500 / TS0 (retention rate) was calculated.

<(3) Flame retardancy>
Based on the UL-94 vertical combustion test, a combustion test was conducted using an injection molded test piece having a thickness of 1.6 mm.
About five test pieces, flame contact was performed twice each, a total of 10 times, the combustion time was measured, and the flame retardance rank based on the standard was displayed.
In order from “V-0”, which is the best, to “V-1” and “V-2”. If it did not correspond to the standard, it was rejected.

<(4) Mold deposit (MD) test>
After the resin composition pellets are dried at 100 ° C. for 4 hours, a test piece for UL94 combustion test using an IS-100GN molding machine manufactured by Toshiba Machine Co., Ltd. (cylinder temperature is set to 300 ° C. and mold temperature is set to 50 ° C.). When molding (thickness 1.6 mm), the mold surface was wiped with ethanol.
Next, 100 shot continuous molding was performed at a pressure of about 1 cm short for complete filling.
Thereafter, the degree of deposits (cloudy) generated at the end of the mold piece cavity of the mold was visually confirmed, and the mold deposit (MD) was evaluated according to the following criteria.
○: Almost no deposit was observed.
Δ: Some deposits were observed.
X: A deposit was clearly seen.

<(5) Releasability>
When a test piece similar to the flame retardant test piece in (3) above is molded, the degree of ease of releasing the test piece and runner from the mold is visually determined according to the following criteria: did.
○: The mold release was good.
(Triangle | delta): Mold release was a little bad.
X: The mold release was very bad.

[Examples 1 to 11], [Comparative Examples 1 to 3]
These were melt-kneaded in accordance with the raw material component composition shown in Tables 1 to 3 below using a twin-screw co-rotating extruder “ZSK-25” manufactured by Coperion, and vacuum degassed from the devolatilization port at the subsequent stage. Resin composition pellets were obtained.
The raw material components other than (D) filler were mixed and supplied from the first supply port of the extruder, and (D) filler was supplied from the second and third supply ports in the middle of the barrel.
The melt-kneading conditions were such that the barrel maximum temperature was set to 260 ° C. and the screw rotation speed was 300 rpm and 15 kg / hr.
The liquid flame retardant (C-5) was supplied and added by a pump from the latter stage after devolatilization.
At this time, 1 part by mass of “Maybrene A3800” manufactured by Mitsubishi Rayon Co., Ltd. containing about 20% polytetrafluoroethylene as a flame retardant aid, and (A), (B), (C ) And 100 parts by weight of the component (D), 0.1 part by weight of the trade name “IRGANOX 1076” manufactured by Ciba Japan Co., Ltd., 0 of the trade name “ADEKA STAB PEP-36” by ADEKA Corporation 0.1 parts by mass and 0.1 part by mass of epoxidized soybean oil (trade name “Kapock S-6” manufactured by Kao Corporation) were mixed and added in a drum blender.
The properties of the obtained resin composition pellets were measured by the evaluation method.
The measurement results are shown in Tables 1 to 3 below.

  In the examples, it has excellent flame retardancy, is excellent in terms of environment and safety and hygiene in production and use, and there is a problem of molded products due to mold contamination and its deposits under severe injection molding conditions. Thus, a resin composition excellent in hygroscopic properties and mechanical properties was obtained.

  The resin composition of the present invention has industrial applicability in a wide range of applications such as various electric / electronic parts, office equipment parts, automobile parts, building materials, other various exterior materials and industrial articles. It is particularly suitable for resin-made mechanical parts for information processing equipment with strict requirements on dimensional characteristics. Examples of resin mechanical parts for information processing equipment include carriages, chassis, gears, shafts, pulleys, etc. in office equipment such as inkjet printers, laser beam printers, copying machines, and fax machines, computers, game machines, music, etc. Optical disc drives for players, video players, AV equipment, etc. (CD-ROM, CD-R, CD-RW, CD-RW, DVD-ROM, DVD-R, DVD-RAM, DVD-RW, DVD + RW, MD, MO) Etc. (pickup chassis, traverse base, sub chassis, base chassis, etc.), trays (disc tray, changer tray, etc.), gears, shafts, pulleys, etc.

Claims (5)

In the total of 100% by mass of the following (A), (B), (C) and (D),
(A) Polycarbonate resin 20-89 mass%,
(B) Styrenic resin 0-30% by mass,
(C) Phosphorus compound having an acid value of 1 or less represented by the following general formula (I): 1 to 30% by mass
as well as,
(D) Inorganic filler 10-60 mass%
A resin composition containing

(In general formula (I), each A is independently selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or 6 to 6 carbon atoms. Represents any one selected from the group consisting of 20 aryl groups and aralkyl groups having 7 to 12 carbon atoms, x and y are each independently an integer of 0 to 4, and n is each Independently 0 or 1 and N is 1 to 30.)   The resin composition according to claim 1, wherein a mass ratio (A) / (B) of the component (A) to the component (B) is 50/50 to 100/0.   The resin composition according to claim 1, wherein the phosphorus compound (C) has an acid value of 0.5 or less. The resin composition according to any one of claims 1 to 3, wherein the phosphorus compound (C) is a phosphorus compound represented by the following general formula (II).

(In formula (II), N is 1-10.)   The resin composition according to any one of claims 1 to 4, wherein the (B) styrene-based resin is a copolymer containing at least styrene and acrylonitrile as monomers.