HK1237807B - Reinforced thermoplastic resin composition and molded article - Google Patents

Abstract

The reinforced thermoplastic resin composition according to the present invention contains, at a specific proportion: a resin main component (C) including 50-100 mass% of a polycarbonate resin (A) and 0-50 mass% of a graft copolymer (B) obtained by polymerizing, in the presence of a rubbery polymer (B1), a monomer mixture containing an aromatic alkenyl compound monomer (a) and a vinyl cyanide compound monomer (b); an inorganic filler (D); a glycidyl ether unit-containing polymer (E) that has a glycidyl ether unit and a mass average molecular weight of 3,800-60,000; and a polyamide 6/66 (F) having a moisture content not higher than 0.1%.

Description

Reinforced thermoplastic resin composition and molded article

Technical Field

The present invention relates to a thermoplastic resin composition reinforced with an inorganic filler and a molded article using the same.

This application claims priority based on Japanese application No. 2015-065828, 3/27 of 2015, the contents of which are incorporated herein by reference.

Background

As a housing material of a mobile device (for example, a personal computer such as a notebook or tablet computer, a mobile phone including a smartphone, a digital camera, a digital video camera, or the like), a thermoplastic resin composition (for example, an ABS resin, a polycarbonate resin/ABS resin, a polyamide resin, or the like) or the thermoplastic resin composition reinforced by an inorganic filler is widely used.

As a method for producing the housing, a method of molding the thermoplastic resin composition by injection molding which can be freely molded into a shape to some extent is generally employed.

In recent years, a case of a portable device is required to be thinner, to be capable of receiving an impact or a load when put in a bag, and to be uncoated for the purpose of reducing the cost. In order to satisfy these requirements, the thermoplastic resin composition for the housing is required to have not only high rigidity and mechanical strength (impact resistance, etc.) after processing the molded article, but also high weld strength, heat resistance, and good moldability at the time of molding.

However, for example, thermoplastic resin compositions such as ABS resins, polycarbonate resins/ABS resins, and polyamide resins polyester resins, which are not reinforced with inorganic fillers, have low rigidity after processing into molded articles, and thus cannot satisfy the demand for making the housing thinner. Further, since polyamide resins have high moisture absorption, warpage, dimensional change, and poor appearance tend to occur with the passage of time after molding.

Therefore, as a thermoplastic resin composition for a housing, a reinforced thermoplastic composition in which an inorganic filler such as glass fiber or carbon fiber is added to an ABS resin or a polycarbonate resin/ABS resin to improve rigidity has been studied.

However, although a reinforced thermoplastic resin composition containing an ABS resin or a polycarbonate resin/ABS resin as a main component has high rigidity and can make a housing thin when formed into a molded article, it has insufficient weld strength and impact resistance when formed into a molded article. On the other hand, a reinforced thermoplastic resin composition containing a polyamide resin as a main component is excellent in weld strength after processing into a molded article, but cannot solve the problem of warpage. This is a problem caused by moisture absorption of a molded article after molding, and no solution to the above problem has been proposed in the past based on studies of molding materials.

As a reinforced thermoplastic resin composition which can give a molded article having good impact resistance, the following is proposed:

(1) a reinforced thermoplastic resin composition comprising an aromatic polycarbonate resin, a graft copolymer, glass fibers surface-treated with a water-soluble polyurethane, a polymer containing a glycidyl ether unit, and a phosphate flame retardant (patent document 1);

(2) a reinforced thermoplastic resin composition comprising an aromatic polycarbonate resin, a fibrous filler surface-treated with polyamide, and a lubricant having a carboxyl group (patent document 2).

As a reinforced thermoplastic resin composition capable of obtaining a molded article having good mechanical strength, the following proposals have been made:

(3) a reinforced thermoplastic resin composition comprising an aromatic polycarbonate resin, a thermoplastic polyester resin, glass fibers surface-treated with a silane coupling agent and an epoxy resin, and a thermoplastic elastomeric polymer (patent document 3);

(4) a reinforced thermoplastic resin composition comprising a polycarbonate resin, a rubber-containing polymer, and carbon fibers bundled with a nylon-based bundling agent (patent document 4).

Documents of the prior art

Patent document 1: JP 2013-14747A

Patent document 2: japanese unexamined patent publication No. 2001-240738

Patent document 3: japanese unexamined patent publication No. 6-49344

Patent document 4: japanese patent laid-open publication No. 60-88062

However, the reinforced thermoplastic resin composition in (1) has insufficient weld strength after processing into a molded article.

(2) The reinforced thermoplastic resin composition of (1) has a problem that mechanical strength other than impact resistance is lowered after processing the molded article.

(3) The reinforced thermoplastic resin composition of (4) or (4) has insufficient impact resistance after processing into a molded article.

In addition to the reinforced thermoplastic resin compositions described in (1) to (4), many reinforced thermoplastic resin compositions have been proposed which are added with an epoxy compound for the purpose of improving the mechanical strength of a molded article.

However, no reinforced thermoplastic resin composition having excellent moldability and a balance among weld strength, mechanical strength and impact resistance of the molded article obtained has been proposed.

Disclosure of Invention

The present invention aims to provide a reinforced thermoplastic resin composition which has good moldability and can improve the weld strength, rigidity, impact resistance, mechanical strength and heat resistance of the obtained molded article, and a molded article having high weld strength, rigidity, impact resistance, mechanical strength and heat resistance.

The present invention includes the following modes.

[1] A reinforced thermoplastic resin composition comprising:

a resin main component (C) comprising 50 to 100 mass% of a polycarbonate resin (A) and 0 to 50 mass% of a graft copolymer (B) (the total of the polycarbonate resin (A) and the graft copolymer (B) being 100 mass%), wherein the graft copolymer (B) is obtained by polymerizing a monomer mixture containing an aromatic alkenyl compound monomer (a) and a vinyl cyanide compound monomer (B) in the presence of a rubbery polymer (B1);

an inorganic filler (D);

a polymer (E) containing a glycidyl ether unit (excluding the graft copolymer (B)) having a glycidyl ether unit and having a mass average molecular weight of 3800 to 60000; and

polyamide 6/66(F) having a water content of 0.1% or less,

the proportion of the inorganic filler (D) is 20 to 50 mass% relative to the total mass (100 mass%) of the reinforced thermoplastic resin composition; the content of the glycidyl ether unit-containing polymer (E) is 1 to 10 parts by mass per 100 parts by mass of the resin main component (C); the polyamide 6/66(F) is contained in an amount of 1 to 15 parts by mass per 100 parts by mass of the resin main component (C).

[2] The reinforced thermoplastic resin composition according to [1], wherein the polyamide 6/66(F) has a relative viscosity of 1.5 to 4.5.

[3] The reinforced thermoplastic resin composition according to [1] or [2], wherein the inorganic filler (D) is a carbon fiber.

[4] The reinforced thermoplastic resin composition according to [1] or [2], wherein the inorganic filler (D) is a glass fiber.

[5] The reinforced thermoplastic resin composition according to any one of [1] to [4], wherein the reinforced thermoplastic resin composition further comprises a phosphate-based flame retardant (G).

[6] The reinforced thermoplastic resin composition according to [5], wherein the phosphate-based flame retardant (G) has a mass-average molecular weight of more than 326.

[7] A molded article obtained by molding the reinforced thermoplastic resin composition according to any one of [1] to [6 ].

Advantageous effects

The reinforced thermoplastic resin composition of the present invention has good moldability, and can improve weld strength, rigidity, impact resistance, mechanical strength and heat resistance of a molded article obtained by molding the resin composition.

The molded article of the present invention has high weld strength, rigidity, impact resistance, mechanical strength and heat resistance.

Detailed Description

The present invention will be described in detail below.

The following "(meth) acrylate" is a generic name of acrylate and methacrylate. The term "molded article" means a molded article obtained by molding the reinforced thermoplastic resin composition of the present invention.

[ reinforced thermoplastic resin composition ]

The reinforced thermoplastic resin composition of the present invention comprises, as essential components: a resin main component (C) containing, as essential components, a polycarbonate resin (A) shown below and, if necessary, a graft copolymer (B); an inorganic filler (D); a polymer (E) containing glycidyl ether units; and polyamide 6/66 (F). Further, preferably, the reinforced thermoplastic resin composition further comprises a phosphate flame retardant (G) and a flame retardant aid (H).

< polycarbonate resin (A) >

The polycarbonate resin (A) is a resin obtained from a dihydroxydiarylalkane. The polycarbonate resin (a) may have a branched structure.

The polycarbonate resin (a) may be used alone or in combination of two or more.

[ Process for producing polycarbonate resin (A) ]

The polycarbonate resin (a) is produced by a known production method. For example, the polycarbonate resin (a) is produced by a method of reacting a dihydroxy or polyhydroxy compound with phosgene or a diester of carbonic acid, a melt polymerization method, or the like. Examples of the dihydroxydiarylalkane include dihydroxydiarylalkanes having an alkyl group at an ortho position to a hydroxyl group. Preferred specific examples of the dihydroxydiarylalkanes include: 4, 4-dihydroxy 2, 2-diphenylpropane (i.e., bisphenol A), tetramethylbisphenol A, or bis (4-hydroxyphenyl) p-diisopropylbenzene, and the like.

For example, the branched polycarbonate resin (a) is produced by substituting a part (for example, 0.2 to 2 mol%) of a dihydroxy compound with a polyhydroxy compound. As specific examples of the polyol compounds, there are enumerated: phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptene, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 1,3, 5-tris (4-hydroxyphenyl) benzene, and the like.

The polycarbonate resin (A) may be recovered from an optical disk or the like.

[ viscosity average molecular weight of polycarbonate resin (A) ]

The viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably 15000 to 35000. When the viscosity average molecular weight of the polycarbonate resin (A) is 15000 or more, the impact resistance of the molded article is higher. If the viscosity average molecular weight of the polycarbonate resin (a) is 35000 or less, the moldability of the reinforced thermoplastic resin composition is higher. The viscosity average molecular weight of the polycarbonate resin (a) is more preferably 17000 to 25000, from the viewpoint that the molded article is particularly excellent in balance among mechanical strength, impact resistance and fluidity of the reinforced thermoplastic resin composition.

The viscosity-average molecular weight of the polycarbonate resin (a) can be determined by a conventionally known method of measuring the solution viscosity. When a commercially available polycarbonate resin (A) is used, a viscosity average molecular weight of a catalog value can also be used.

[ proportion of polycarbonate resin (A) ]

The proportion of the polycarbonate resin (A) in the resin main component (C) (100 mass%) is 50 to 100 mass%, preferably 80 to 95 mass%. When the proportion of the polycarbonate resin (a) is 50% by mass or more, the impact resistance of the molded article is improved. When the proportion of the polycarbonate resin (a) is 95% by mass or less, the moldability of the reinforced thermoplastic resin composition is further improved.

< graft copolymer (B) >

The graft copolymer (B) is obtained by polymerizing a monomer mixture containing an aromatic alkenyl compound monomer (a) and a vinyl cyanide compound monomer (B) in the presence of a rubbery polymer (B1), and is a polymer obtained by grafting a molecular chain (B2) containing an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit to the rubbery polymer (B1).

More specifically, the graft copolymer (B) is obtained by bonding molecular chains (B2) containing units of an aromatic vinyl compound monomer (a) and a vinyl cyanide compound monomer (B) to particles of a rubbery polymer (B1) having a volume average particle diameter of 0.1 to 0.6 [ mu ] m, and comprises a rubber part composed of the rubbery polymer (B1) and an outer layer part composed of units of the aromatic vinyl compound monomer (a) and the vinyl cyanide compound monomer (B).

The graft copolymer (B) may be used alone or in combination of two or more.

[ rubbery Polymer (B1) ]

Examples of the rubbery polymer (B1) include butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, isoprene rubber, chloroprene rubber, isobutylene rubber, ethylene-propylene rubber, acrylic rubber, ethylene-propylene-non-conjugated diene rubber, epichlorohydrin rubber, diene-acrylic composite rubber, silicone (polysiloxane) -acrylic composite rubber, and the like. Among these, from the viewpoint of good plating performance of the molded article, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, diene-acrylic composite rubber, silicone-acrylic composite rubber; from the viewpoint of the favorable molded product, a silicone-acrylic composite rubber is preferable.

(diene-acrylic acid compounded rubber)

The diene component in the diene-acrylic composite rubber includes 50 mass% or more of a butadiene unit. Examples of the diene component include: butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, or the like.

The acrylic rubber component in the diene-acrylic composite rubber is a component obtained by polymerizing an alkyl (meth) acrylate (f) and a polyfunctional monomer (g).

Examples of the alkyl (meth) acrylate (f) include: alkyl acrylates (methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc.) or alkyl methacrylates (hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, etc.). The alkyl (meth) acrylate (f) may be used alone or in combination of two or more.

Examples of the polyfunctional monomer (g) include: allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol dimethacrylate, triallyl cyanurate or triallyl isocyanurate. The polyfunctional monomer (g) may be used alone or in combination of two or more.

As the composite structure of the diene-acrylic composite rubber, there are listed: the periphery of the diene component is covered with a core-shell structure of an acrylic rubber component; a core-shell structure of diene component is covered around the acrylic rubber component; a structure in which a diene component and an acrylic rubber component are interlaced with each other; a copolymer structure in which diene monomer units and alkyl (meth) acrylate monomer units are randomly arranged.

(Silicone-acrylic composite rubber)

The silicone component of the silicone-acrylic composite rubber contains polyorganosiloxane as a main component. The silicone component is preferably a polyorganosiloxane containing a vinyl-polymerizable functional group.

The acrylic rubber component of the silicone-acrylic composite rubber is the same as that of the diene-acrylic composite rubber.

As the composite structure of the silicone-acrylic composite rubber, there are listed: the periphery of the organic silicon component is covered with a core-shell structure of an acrylic rubber component; a core-shell structure of an organic silicon component covers around the acrylic rubber component; a structure in which the silicone component and the acrylic rubber component are interlaced with each other; a structure in which polyorganosiloxane fragments and polyalkyl (meth) acrylate fragments are linearly and sterically bonded to each other to form a network rubber structure, and the like

(method for producing rubbery Polymer (B1))

The rubber polymer (B1) is prepared, for example, by emulsion polymerization of a monomer which forms the rubber polymer (B1) in the presence of a radical polymerization initiator. The particle size of the rubbery polymer (B1) can be easily controlled by the method of preparing the emulsion polymerization.

The volume average particle diameter of the rubbery polymer (B1) is preferably 0.1 to 0.6. mu.m, from the viewpoint of further improving the impact resistance of the molded article.

In the present invention, the volume average particle diameter is a value measured by a method such as a laser diffraction and scattering method.

(content of rubbery Polymer (B1))

The content of the rubbery polymer (B1) in the resin main component (C) (100 mass%) is preferably 0.5 to 3.5 mass%. When the content of the rubbery polymer (B1) is 0.5% by mass or more, the impact resistance of the molded article is further improved. When the content of the rubbery polymer (B1) is 3.5% by mass or less, the moldability of the reinforced thermoplastic resin composition becomes further favorable and the appearance of the molded article becomes favorable.

[ molecular chain (B2) ]

The molecular chain (B2) contains an aromatic vinyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit as essential components, and contains another monomer (c) unit copolymerizable with these as an optional component. From the viewpoint of a good balance between the impact resistance of the molded article and the moldability of the reinforced thermoplastic resin composition, the proportion of the aromatic vinyl compound monomer (a) unit is preferably 50 to 90% by mass, the proportion of the vinyl cyanide compound monomer (b) unit is preferably 10 to 50% by mass, and the proportion of the other monomer (c) unit is preferably 0 to 40% by mass (although the total of the proportions of the monomers (a) to (c) is 100% by mass).

examples of the aromatic alkenyl compound monomer (a) include styrene, α -methylstyrene, and vinyltoluene, and among these, styrene is preferred.

Examples of the vinyl cyanide compound monomer (b) include acrylonitrile and methacrylonitrile, and among these, acrylonitrile is preferred.

Examples of the other monomer (c) include: alkyl methacrylates (methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, etc.), alkyl acrylates (methyl acrylate, ethyl acrylate, butyl acrylate, etc.), maleimide compounds (N-phenylmaleimide, etc.), and the like.

[ acetone-insoluble portion and acetone-soluble portion of graft copolymer (B) ]

The graft copolymer (B) preferably comprises 70 to 99 mass% of an acetone-insoluble portion, and the reduced viscosity of a 0.2g/dl N, N-dimethylformamide solution of the acetone-soluble portion measured at 25 ℃ is 0.3 to 0.7 dl/g.

When the acetone-insoluble fraction is 70% by mass or more, the surface appearance of the molded article is good, and the moldability of the reinforced thermoplastic resin composition is further good. When the acetone-insoluble portion in the acetone solvent is 99% by mass or less, the tear strength of the molded article is improved.

When the reduced viscosity of the acetone-soluble portion is 0.3dl/g or more, the tear strength of the molded article is improved. When the reduced viscosity of the acetone-soluble portion is 0.7dl/g or less, the surface appearance of the molded article is good, and the moldability of the reinforced thermoplastic resin composition is further good.

The reduced viscosity in the present invention can be determined by the same method as the viscosity average molecular weight, for example, the method of measuring the solution viscosity.

The acetone soluble fraction was measured as follows.

2.5g of the graft copolymer was immersed in 90ml of acetone, heated at 65 ℃ for 3 hours, and then centrifuged at 1500rpm for 30 minutes using a centrifuge. Then, the supernatant was removed, the residue was dried at 65 ℃ for 12 hours with a vacuum drier, and the dried sample was precisely weighed. The acetone-soluble fraction (%) of the graft copolymer was determined from the mass difference (2.5 g-mass of dried sample). The reduced viscosity of the acetone-soluble fraction was a 0.2g/dl solution in N, N-dimethylformamide measured at 25 ℃.

The acetone-soluble portion is the same polymer as the molecular chain (B2), and means a polymer to which the rubbery polymer (B1) is not grafted. The acetone-soluble portion is often formed simultaneously when the molecular chain (B2) is grafted to the rubbery polymer (B1). Thus, the graft copolymer (B) comprises an acetone-insoluble portion and an acetone-soluble portion.

[ Process for producing graft copolymer (B) ]

The graft copolymer (B) is obtained by polymerizing the aromatic vinyl compound monomer (a) and the vinyl cyanide compound monomer (B), and optionally the other monomer (c), in the presence of the rubbery polymer (B1).

The graft polymerization process is preferably an emulsion polymerization process. In the graft polymerization, various chain transfer agents may be added to adjust the molecular weight, graft ratio, and reduced viscosity of the acetone-soluble portion of the graft copolymer (B).

[ proportion of graft copolymer (B) ]

The proportion of the graft copolymer (B) in the resin main component (C) (100 mass%) is 0 to 50 mass%, preferably 5 to 20 mass%. When the proportion of the graft copolymer (B) is 5% by mass or more, the moldability of the reinforced thermoplastic resin composition is further improved. When the proportion of the graft copolymer (B) is 50% by mass or less, the impact resistance of the molded article is improved. When the proportion of the graft copolymer (B) is 0% based on 100% by mass of the resin main component (C), the proportion of the polycarbonate resin (a) becomes 100% by mass.

< inorganic Filler (D) >

Examples of the inorganic filler (D) include: glass fibers; inorganic fibers such as carbon fibers; coating metal in inorganic fiber; inorganic substances such as wollastonite, talc, mica, glass flake, glass bead, potassium titanate, calcium carbonate, magnesium carbonate, carbon black, and ketjen black; metals or alloys such as iron, copper, zinc, aluminum, etc.; and fibers, powders, etc. of their oxides. Among these, glass fiber and carbon fiber are preferably used in view of obtaining high rigidity by a low compounding ratio.

The inorganic filler (D) may be used alone or in combination of two or more.

The inorganic fibers, the fibers or powders of the inorganic fibers coated with a metal, an inorganic substance, a metal or an alloy, or an oxide thereof may be treated with a known coupling agent (e.g., a silane coupling agent or a titanate coupling agent) or other surface treatment agent on the surface thereof.

In addition, the glass fibers and carbon fibers may be coated or bundled with thermoplastic resins such as ethylene/vinyl acetate copolymer and polyamide; such as a thermosetting resin such as a polyurethane resin or an epoxy resin.

The ratio of the major diameter to the minor diameter (major diameter/minor diameter) in the fiber cross section of the glass fiber or the carbon fiber is preferably 1 to 6, and more preferably 2 to 4. When the major/minor diameter is 1 or more, good impact properties and strength are obtained. When the major/minor diameter is 6 or less, good moldability (extrusion workability) is obtained.

The long diameter/short diameter in the fiber section can be determined by observing arbitrary 8 positions of the fiber section with an electron microscope, for example, and averaging the long diameter/short diameter at the arbitrary 8 positions. When a commercially available product is used, the long diameter/short diameter of the cross section of the fiber can be used in the catalog value.

The glass fiber or the carbon fiber may be either a long fiber or a short fiber. The glass fiber or the carbon fiber is preferably a short fiber having low anisotropy, and more preferably a chopped fiber.

The inorganic filler (D) may be used alone or in combination of two or more.

[ proportion of inorganic Filler (D) ]

The proportion of the inorganic filler (D) is 20 to 50% by mass, preferably 30 to 45% by mass, based on the total mass (100% by mass) of the reinforced thermoplastic resin composition. When the proportion of the inorganic filler (D) is 20% by mass or more, the rigidity of the molded article is improved. When the proportion of the inorganic filler (D) is 50% by mass or less, the moldability of the reinforced thermoplastic resin composition is good.

< glycidyl ether Unit-containing Polymer (E) >

The polymer (E) containing a glycidyl ether unit is a polymer having a glycidyl ether unit in the molecule. The glycidyl ether unit-containing polymer (E) does not include a polymer having a halogen atom (bromine, etc.) or a block type polymer.

Examples of the polymer (E) containing a glycidyl ether unit include glycidyl ether type epoxy resins obtained by reacting a compound having a hydroxyl group with epichlorohydrin.

Examples of the glycidyl ether type epoxy resin include polymer materials such as bisphenol type epoxy resins, novolak type epoxy resins, polyglycidyl ethers of aliphatic polyhydric alcohols, biphenyl type epoxy resins, and the like, and molecular chains (for example, epoxy group-containing phenoxy resins) containing a repeating unit represented by the following formula (2) in the molecule are exemplified.

[ chemical formula 1]

However, m is an integer of 1 or more.

m is preferably 13 to 211, more preferably 19 to 176.

Examples of the bisphenol epoxy resin include bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, and epoxy resin having a structure of bisphenol a and bisphenol F.

Examples of the novolak type epoxy resin include a phenol novolak type epoxy resin and a cresol novolak type epoxy resin.

Examples of the polyglycidyl ethers of aliphatic polyhydric alcohols include: alkylene glycol diglycidyl ethers (such as ethylene glycol diglycidyl ether and the like), polyoxyalkylene glycol diglycidyl ethers (such as diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and the like), glycerol triglycidyl ether, and the like.

The glycidyl ether unit-containing polymer (E) is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, an epoxy resin having a structure of bisphenol a and bisphenol F, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, an epoxy group-containing phenoxy resin, or the like, from the viewpoint of further improving the mechanical strength of a molded article.

The polymer (E) containing a glycidyl ether unit may be liquid, semisolid or solid at ordinary temperature (20 ℃ C.). The polymer (E) containing a glycidyl ether unit is preferably a solid in view of workability in mixing and kneading.

The glycidyl ether type epoxy resin may be used alone or in combination of two or more.

[ Mass average molecular weight of the glycidyl ether unit-containing Polymer (E) ]

The mass average molecular weight of the polymer (E) containing a glycidyl ether unit is 3800 to 60000, preferably 5500 to 50000. When the mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 3800 or more, the impact resistance and mechanical strength of the molded article are improved. When the mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 60000 or less, the reinforced thermoplastic resin composition is excellent in moldability.

The mass average molecular weight of the glycidyl ether unit-containing polymer (E) can be determined by a conventionally known mass analysis method. When the polymer (E) containing a glycidyl ether unit is commercially available, the mass average molecular weight can be used according to the trade name.

[ method for obtaining Polymer (E) containing glycidyl Ether Unit ]

Examples of the commercially available glycidyl ether unit-containing polymer (E) include JER (registered trademark) series manufactured by mitsubishi chemical corporation, EPOTOHTO (registered trademark) series manufactured by juitangsu chemical corporation, phenotol tate (registered trademark) series, AER (registered trademark) series manufactured by asahi chemical and electronic materials, and EPICLON (registered trademark) series manufactured by DIC corporation.

[ content of the glycidyl ether Unit-containing Polymer (E) ]

The content of the glycidyl ether unit-containing polymer (E) is 1 to 10 parts by mass, preferably 3 to 8 parts by mass, per 100 parts by mass of the resin main component (C). When the content of the glycidyl ether unit-containing polymer (E) is 1 part by mass or more per 100 parts by mass of the resin main component (C), the mechanical strength, impact resistance, and weld strength of the molded article are improved. When the content of the glycidyl ether unit-containing polymer (E) is 10 parts by mass or less with respect to 100 parts by mass of the resin main component (C), moldability of the reinforced thermoplastic resin composition is good.

< Polyamide 6/66(F) >

Polyamide 6/66(F) is a copolymer of polycaprolactam (polyamide 6) and polyhexamethylene adipamide (polyamide 66) (polyamide 6/66 copolymer).

Polyamide 6/66(F) is obtained by copolymerizing epsilon-caprolactam, hexamethylenediamine and adipic acid.

The polyamide 6/66(F) preferably contains a large amount of polycaprolactam (polyamide 6), and specifically preferably contains 55 to 95 mass% of caprolactam units and 5 to 45 mass% of hexamethylene adipamide units, based on 100 mass% of the total of the caprolactam units and the hexamethylene adipamide units. When the caprolactam unit content is 55% by mass or more, the weld strength of the molded article is further improved; when the caprolactam unit content is 95% by mass or less, the moldability of the reinforced thermoplastic resin composition is further improved.

The polyamide 6/66(F) has a water content of 0.1% or less. When polyamide 6/66 having a water content of more than 0.1% is used, the weld strength and heat resistance are reduced. Generally, polyamide resins have water absorption properties, and therefore have different water contents depending on storage methods and conditions, storage periods, and differences between production lots.

Therefore, in the present invention, the polyamide 6/66(F) was used after the water content thereof was measured and confirmed.

[ relative viscosity of Polyamide 6/66(F) ]

The relative viscosity of the polyamide 6/66(F) is preferably 1.5 to 4.5, more preferably 2.0 to 4.0, and still more preferably 2.5 to 3.5. When the relative viscosity of polyamide 6/66(F) is 1.5 or more, the weld strength of the molded article is further improved. When the relative viscosity of the polyamide 6/66(F) is 4.5 or less, the moldability is further improved.

The relative viscosity of polyamide 6/66(F) can be determined, for example, by using a 96 mass% sulfuric acid solution (concentration: 1.0g/dl) at 25 ℃ with an Ostwald viscometer. When a commercially available polyamide 6/66(F) is used, the relative viscosity of the catalog value can be used.

[ content of Polyamide 6/66(F) ]

The content of polyamide 6/66(F) is 1 to 15 parts by mass, preferably 3 to 10 parts by mass, per 100 parts by mass of the resin main component (C). When the content of polyamide 6/66(F) is 1 part by mass or more per 100 parts by mass of the resin main component (C), the weld strength of the molded article is improved. When the content of polyamide 6/66(F) is 15 parts by mass or less with respect to 100 parts by mass of the resin main component (C), a decrease in the weld strength and warpage of a molded article can be suppressed.

< flame retardant >

The reinforced thermoplastic resin composition of the present invention may contain a flame retardant.

Examples of the flame retardant include a phosphate flame retardant (G) and a known non-halogen flame retardant.

[ phosphoric acid ester flame retardant (G) ]

The phosphate flame retardant (G) may be a compound represented by the following formula (2).

[ chemical formula 2]

However, R¹、R²、R³、R⁴Each independently is a hydrogen atom or an organic group, R¹、R²、R³、R⁴Not both hydrogen atoms, A is an organic group of more than two valences; p is 0 or 1; q is an integer of 1 or more; r is an integer of 0 or more.

As organic groups, mention may be made of: an alkyl group which may be substituted (e.g., methyl, ethyl, butyl, octyl, etc.); cycloalkyl groups (e.g., cyclohexyl, etc.); or an aryl group (e.g., phenyl, or alkyl-substituted phenyl, etc.). The number of substituents in substitution is not particularly limited as long as it is chemically allowable. As substituted organic groups, mention may be made of: such as alkoxy, alkylthio, aryloxy, or arylthio, and the like. These substituents may be combined (e.g., arylalkoxyalkyl group, etc.), or may be combined by bonding these substituents through an oxygen atom, a nitrogen atom, a sulfur atom, etc. (e.g., arylsulfonylalkyl group, etc.).

The divalent or higher organic group means a divalent or higher functional group obtained by further removing two or more hydrogen atoms bonded to carbon atoms from the organic group. Examples thereof include alkylene groups and (substituted) phenylene groups. The position of the hydrogen atom removed from the carbon atom is arbitrary. A is preferably a divalent organic group.

Specific examples of the phosphate flame retardant (G) include: trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trihexyl phosphate, cresyldiphenyl phosphate, hexyldiphenyl phosphate, octyldiphenyl phosphate, diphenyl-2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, resorcinol diphenyl phosphate, polyphosphate (bisphenol a diphosphate, hydroquinone diphosphate, resorcinol diphosphate, trisphenol triphosphate, bisphenol a bis (xylylphosphate), bisphenol a bis (diphenyl phosphate), phenylene bis (xylylphosphate), phenylene bis (dixylylphosphate), or phenylene bis (dixylylphosphate)).

The phosphate flame retardant (G) is preferably triphenyl phosphate, bisphenol A bis (diphenyl phosphate), phenylene bis (diphenyl phosphate) or phenylene bis (dixylyl) phosphate among the above.

Polyphosphate esters are obtained by dehydration condensation of various diols such as polynuclear phenols (e.g., bisphenol a) and orthophosphoric acid. Examples of the diol include hydroquinone, resorcinol, dihydroxyphenyl methane, dihydroxyphenyl dimethyl methane, dihydroxydiphenyl, p' -dihydroxydiphenyl sulfone, and dihydroxynaphthalene.

(Mass average molecular weight of phosphate flame retardant (G))

The mass average molecular weight of the phosphate flame retardant (G) is preferably 326 or more, more preferably 326 or more, and particularly preferably 550 or more. When the phosphate flame retardant (G) having a mass average molecular weight of more than 326 is used, the moldability of the reinforced thermoplastic resin composition is further improved, and a molded article having an excellent appearance can be obtained. From the viewpoint of flame retardancy of the molded article, the upper limit of the mass average molecular weight of the phosphate flame retardant (G) is preferably 692 or less, more preferably 690 or less, and particularly preferably 686 or less.

The mass average molecular weight of the phosphate flame retardant (G) can be obtained by a conventionally known mass analysis method. When a commercially available phosphate flame retardant (G) is used, the mass average molecular weight can be determined by the catalog value.

(method for obtaining phosphate flame retardant (G))

Examples of commercially available phosphate flame retardants (G) include FP series manufactured by ADEKA, CRONIX (registered trademark) series manufactured by Ajinomoto Fine Technics, Reofasu (registered trademark) series manufactured by Chemtura Japan, CR series manufactured by Dai eight chemical company, and PX series.

(content of phosphate flame retardant (G))

The content of the phosphate flame retardant (G) is preferably 1 to 25 parts by mass, more preferably 3 to 23 parts by mass, per 100 parts by mass of the resin main component (C). When the content of the phosphate flame retardant (G) is 1 part by mass or more per 100 parts by mass of the resin main component (C), the moldability of the molded article is further improved. When the content of the phosphate flame retardant (G) is 25 parts by mass or less with respect to 100 parts by mass of the resin main component (C), the impact resistance of the molded article is further improved.

[ non-halogen flame retardants ]

Examples of the non-halogen flame retardant include inorganic flame retardants such as phosphazenes, phosphorus-containing polyesters, red phosphorus, and aluminum hydroxide.

As the red phosphorus flame retardant, a red phosphorus flame retardant stabilized by coating with a thermosetting resin or a red phosphorus flame retardant stabilized by coating with a thermosetting resin and a metal hydroxide is used. The red phosphorus flame retardant alone is flammable, and therefore at least a part of the resin main component (C) or the polycarbonate resin (a) may be mixed in advance as a master batch.

< flame retardant auxiliary (H) >

The reinforced thermoplastic resin composition of the present invention may contain a flame retardant auxiliary (H) for preventing dripping during burning. Examples of the flame retardant auxiliary (H) include polytetrafluoroethylene, a compound having a tetrafluoroethylene unit, and a silicone polymer.

When polytetrafluoroethylene or a compound having a tetrafluoroethylene unit is mixed as the flame-retardant auxiliary (H), the content of the flame-retardant auxiliary (H) is preferably 1 part by mass or less with respect to 100 parts by mass of the resin main component (C) from the viewpoint of the surface appearance of a molded article.

< other ingredients >

The reinforced thermoplastic resin composition of the present invention may be mixed with other modifiers, mold release agents, light-or heat-resistant stabilizers, antistatic agents, dyes, pigments, and the like, as required.

< method for producing reinforced thermoplastic resin composition >

The reinforced thermoplastic resin composition of the present invention is obtained by mixing a polycarbonate resin (a), if necessary, a graft copolymer (B), an inorganic filler (D), a glycidyl ether unit-containing polymer (E), polyamide 6/66(F), and if necessary, a flame retardant aid (H), or other components. Specifically, the above components are mixed by using a mixing device (for example, henschel mixer, tumbler mixer, nauta mixer, etc.). Further, the kneading may be carried out using a kneading apparatus (for example, a single-screw extruder, a twin-screw extruder, a banbury mixer, a co-kneader, or the like).

< Effect >

The reinforced thermoplastic resin composition of the present invention described above contains the polycarbonate resin (a), the graft copolymer (B), the inorganic filler (D), the glycidyl ether unit-containing polymer (E), and the polyamide 6/66(F) in a specific ratio, and therefore, has good moldability, and can improve the weld strength, rigidity, impact resistance, mechanical strength, or heat resistance of the resulting molded article.

Further, the reinforced thermoplastic resin composition of the present invention was prepared into a molded article having a length of 210mm, a width of 297mm and a thickness of 1mm by drying pellets obtained by melt-kneading using a twin-screw extruder at 100 ℃ for 3 hours and then molding the dried pellets by an injection molding machine under molding conditions of a molding temperature of 290 ℃, an injection speed of 99% and a mold temperature of 85 ℃. The welding strength of the molded product is obtained by measuring a test force (N) when a welding point in the molded product is pressed by a terminal at one point to generate a crack; the welding strength is preferably 189(N) or more, and more preferably 202 to 260 (N). If the welding strength is above the lower limit, the occurrence of cracks at the welding point can be suppressed when a weight or impact is applied after the molded article is processed; when the welding strength is not more than the above upper limit, the balance with other characteristics is good.

In the reinforced thermoplastic resin composition of the present invention, the molded article obtained under the above-mentioned conditions preferably has a Charpy impact strength of 8 (kJ/m) measured in accordance with ISO179²) More preferably 10 to 21 (kJ/m) or more²). When the charpy impact strength is not less than the lower limit value, the impact resistance is sufficiently excellent; when the charpy impact strength is not more than the above upper limit value, the balance with other characteristics is good.

In the reinforced thermoplastic resin composition of the present invention, the molded article obtained under the above conditions preferably has a flexural strength measured in accordance with ISO178 of 108(MPa) or more, more preferably 133 to 265 (MPa). Also, the flexural modulus measured in accordance with ISO178 as described above is preferably 4100(MPa) or more, more preferably 5100 to 14600 (MPa). When the bending strength is not less than the lower limit, the mechanical strength is excellent; when the bending strength is not more than the above upper limit, the balance with other characteristics is good. When the flexural modulus is not less than the lower limit, the rigidity is excellent; when the flexural modulus is not more than the above upper limit, the balance with other properties is good.

In the reinforced thermoplastic resin composition of the present invention, the molded article obtained under the above conditions has a deflection temperature as an index of heat resistance of preferably 91 (. degree. C.) or more, more preferably 94 to 130 (. degree. C.) as measured by ISO75 and 1.80MPa weight flat pressing method. When the deflection temperature is not less than the lower limit, the heat resistance is sufficiently excellent; when the deflection temperature is not more than the above upper limit, the balance with other characteristics is good.

In the reinforced thermoplastic resin composition of the present invention, the molded article obtained under the above conditions is preferably not more than 1mm in warpage amount, more preferably not more than 0.8mm, after being immersed in water for two days. If the amount of warpage is not more than 1mm, the dimensional and shape stability is excellent.

[ molded article ]

The molded article of the present invention is a product obtained by molding the reinforced thermoplastic resin composition of the present invention.

Examples of the molding method of the reinforced thermoplastic resin composition include: injection molding (including insert molding of films, glass plates, and the like), injection compression molding, extrusion, blow molding, vacuum molding, pressure molding, calendering, inflation, and the like. Among them, the injection molding method or the injection compression molding method is preferable because a molded product having excellent mass productivity and high dimensional accuracy can be obtained.

The molded article of the present invention can be suitably used for housings of personal computers (including notebook and tablet computers), projectors (including liquid crystal projectors), televisions, printers, facsimiles, copiers, audio devices, game machines, cameras (including video cameras, digital cameras, and the like), video devices (video recorders, and the like), musical instruments, mobile devices (electronic notebooks, Personal Digital Assistants (PDAs), and the like), lighting devices, communication devices (including mobile phones, smartphone phones, and the like), fishing tackle, game machine devices (pachinko products, and the like), vehicle products, furniture products, sanitary products, building materials, and the like. Among these applications, the present invention is particularly advantageous for use in housings of mobile devices (e.g., personal computers including notebooks and tablets, and portable devices including smartphones).

The molded article of the present invention is a product obtained by molding the reinforced thermoplastic resin composition of the present invention, and therefore, as described above, is excellent in weld strength, rigidity, impact resistance, mechanical strength, and heat resistance.

Examples

The following specifically shows examples. The present invention is not limited to these examples. The terms "part" and "%" described below mean "part by mass" and "% by mass", respectively.

< measuring method, evaluation method >

[ acetone-soluble portion ]

2.5g of the graft copolymer was immersed in 90ml of acetone, heated at 65 ℃ for 3 hours, and then centrifuged at 1500rpm for 30 minutes using a centrifuge. Then, the supernatant was removed, the residue was dried at 65 ℃ for 12 hours with a vacuum drier, and the dried sample was precisely weighed. The acetone-soluble fraction (%) of the graft copolymer was determined from the mass difference (2.5 g-mass of dried sample). The reduced viscosity of the acetone-soluble fraction was 0.2g/dl of N, N-dimethylformamide solution measured at 25 ℃.

[ Charpy impact Strength ]

The Charpy impact strength was measured in accordance with ISO 179.

[ flexural Strength and flexural modulus ]

The flexural strength and flexural modulus of elasticity were measured in accordance with ISO 178. The flexural strength is an index of mechanical strength of a molded article, and the flexural modulus is an index of rigidity of a molded article.

[ welding Strength ]

A4-sized liquid crystal display cover (thickness: 1mm) of a notebook personal computer was molded by an injection molding machine (product of Japan Steel works, J350E, 350t Accelerator) under molding conditions of a molding temperature of 290 ℃, an injection speed of 99% and a mold temperature of 85 ℃. The test force (N) at the time of occurrence of a crack was measured by pressing the welded point of the molded article at one point with a terminal, and this was taken as the welding strength.

[ Heat resistance ]

The deflection temperature was measured according to ISO75 by the 1.80MPa load leveling method.

[ formability ]

A liquid crystal display panel cover (thickness 1mm) of a notebook personal computer of size A4 was molded by the same method as that in the evaluation of the weld strength. Moldability was evaluated according to the following criteria based on whether there was short shot (unfilled portion) at the time of molding and whether sink marks and gas scorch occurred.

excellent performance, no unfilled, sink mark and gas scorch.

A part of the test piece was found to be sink mark.

X: not filled, or gas was found to be charred.

[ warping ]

A liquid crystal display panel cover (thickness 1mm) of a notebook personal computer of size A4 was molded by the same method as that in the evaluation of the weld strength. The obtained molded article (liquid crystal display panel cover) was immersed in water for two days, and then compared with the molded article before immersion, the warpage amount was evaluated according to the following criteria.

the warpage amount is not more than 1 mm.

X: the warping amount is more than 1 mm.

< ingredients >

[ polycarbonate resin (A) ]

OVAREX7021PJ (viscosity average molecular weight: 18800) manufactured by Mitsubishi engineering plastics was used as the polycarbonate resin (A-1).

[ production of graft copolymer (B-1) ]

To a polybutadiene latex having a solid content concentration of 35% and a volume average particle diameter of 0.08 μm (solid content: 100 parts), a copolymer latex having a volume average particle diameter of 0.08 μm composed of 85% of n-butyl acrylate units and 15% of methacrylic acid units (solid content: 2 parts) was added with stirring. Then, it was stirred for 30 minutes to obtain an enlarged butadiene rubbery polymer (B1-1) latex having a volume average particle diameter of 0.28. mu.m.

The resultant enlarged butadiene rubbery polymer (B1-1) latex was charged into a reactor, to which were added 100 parts of distilled water, 4 parts of wood rosin emulsifier, 0.4 part of demon N (manufactured by kao corporation, naphthalenesulfonic acid formalin condensate), 0.04 part of sodium hydroxide, and 0.7 part of dextrose. Then, the temperature was raised while stirring, 0.1 part of ferrous sulfate, 0.4 part of sodium pyrophosphate, and 0.06 part of sodium hydrosulfite were added at a time point of an internal temperature of 60 ℃, and then a mixture including the following components was continuously dropped over 90 minutes, followed by holding for 1 hour and cooling.

The resulting graft copolymer (B-1) latex was coagulated with dilute sulfuric acid, washed, filtered and dried to obtain a dry powder of the graft copolymer (B-1).

The acetone-soluble portion of the graft copolymer (B-1) was 27%. Also, the reduced viscosity of the acetone-soluble portion was 0.3 dl/g.

[ production of graft copolymer (B-2) ]

The raw materials were charged into the reactor in the following proportions, and the mixture was stirred at 50 ℃ for 4 hours under nitrogen exchange to conduct polymerization, thereby obtaining a rubbery polymer (B1-2) latex.

The resulting latex (solid content: 100 parts) of the rubbery polymer (B1-2) was charged into another reactor, diluted with 280 parts of ion-exchanged water, and heated to 70 ℃.

In addition, 0.7 part of benzoyl peroxide was dissolved in 100 parts of a monomer mixture consisting of acrylonitrile/styrene (mass ratio) 29/71, and nitrogen substitution was performed. Then, the monomer mixture was fed at a rate of 30 parts/hr to a reactor containing the above latex of the rubbery polymer (B1-2) by means of a metering pump. After the monomer mixture was completely added, the temperature of the reactor was raised to 80 ℃ and stirring was continued for 30 minutes to obtain a latex of the graft copolymer (B-2). The polymerization rate was 99%.

The graft copolymer (B-2) latex was charged while stirring into 0.15% aluminum chloride (AlCl) in an amount 3 times the amount of the whole latex₃·6H₂O) an aqueous solution (90 ℃ C.) was solidified in a solidification tank. After all the whole latex was added, the temperature in the coagulation tank was raised to 93 ℃ and left as it is for 5 minutes to cool. Then, the resulting mixture was dehydrated by a centrifugal separator, washed and dried to obtain a dry powder of the graft copolymer (B-2).

The acetone-soluble portion of the graft copolymer (B-2) was 21%. And the reduced viscosity of the acetone-soluble portion was 0.7 dl/g.

[ production of graft copolymer (B-3) ]

A graft copolymer (B-3) comprising a polybutadiene/polybutylacrylate compounded rubber as the rubbery polymer (B1-3) was obtained by the following method.

To a polybutadiene latex having a solid content concentration of 35% and a volume average particle diameter of 0.08 μm (solid content of 20 parts), a copolymer latex having an average particle diameter of 0.10 μm (solid content of 0.4 part) composed of 82% of n-butyl acrylate units and 18% of methacrylic acid units was added with stirring. This was stirred for 30 minutes to obtain an enlarged diene rubber latex having a volume average particle diameter of 0.36. mu.m.

The obtained enlarged diene rubber latex (solid content: 20 parts) was charged into a reactor, and 1 part of potassium disproportionated rosin acid, 150 parts of ion-exchanged water and a monomer mixture having the following composition were added thereto, nitrogen substitution was performed, and the temperature was raised to 50 ℃ (internal temperature).

80 portions of n-butyl acrylate

0.32 part of allyl methacrylate

Ethylene glycol dimethacrylate 0.16 part

Then, a solution prepared by dissolving 0.0002 part of ferrous sulfate, 0.0006 part of disodium ethylenediaminetetraacetate, and 0.25 part of rongalite in 10 parts of ion-exchange water was added to the reactor and reacted. The internal temperature at the end of the reaction was 75 ℃. Further, the temperature was raised to 80 ℃ and the reaction was continued for 1 hour to obtain a rubbery polymer (B1-3) latex composed of an enlarged composite rubber of a diene rubber and a polybutyl acrylate rubber. The polymerization rate in this case was 98.8%.

The rubbery polymer (B1-3) latex (50 parts in solid content) was charged into a reactor, diluted with 140 parts of ion-exchanged water, and the temperature was raised to 70 ℃.

In addition, 0.35 part of benzoyl peroxide was dissolved in 50 parts of a monomer mixture consisting of acrylonitrile/styrene (mass ratio) 29/71, and after nitrogen substitution, the monomer mixture was added at 15 parts/hr by a metering pump to a reactor containing the latex of the rubbery polymer (B1-3). After the monomer mixture was completely added, the temperature of the reactor was raised to 80 ℃ and stirring was continued for 30 minutes to obtain a latex of the graft copolymer (B-3). The polymerization rate in this case was 99%.

The graft copolymer (B-3) latex was put into a coagulation vessel containing a 0.5% aqueous solution of sulfuric acid (90 ℃ C.) in an amount 3 times that of the whole latex while stirring, and was coagulated. After all the whole latex was added, the temperature in the coagulation tank was raised to 93 ℃ and left as it is for 5 minutes to cool. Then, the resulting mixture was dehydrated by a centrifugal separator, washed and dried to obtain a dry powder of the graft copolymer (B-3).

The acetone-soluble portion of the graft copolymer (B-3) was 20%. And the reduced viscosity of the acetone-soluble portion was 0.7 dl/g.

[ production of graft copolymer (B-4) ]

A graft copolymer (B-4) comprising a silicone rubber/polybutyl acrylate composite rubber as the rubbery polymer (B1-4) was obtained by the following method.

96 parts of octamethylcyclotetrasiloxane, 2 parts of gamma-methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane-based mixture. To the siloxane mixture, 300 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved was added, and after stirring for 2 minutes at 10000rpm in a high-speed stirrer, the mixture was passed through the stirrer once at a pressure of 30MPa to obtain a stable premixed organosiloxane latex.

In a reactor including a reagent injection container, a cooling tube, a water jacket heating furnace and a stirring device, 2 parts of dodecylbenzenesulfonic acid and 98 parts of distilled water were injected to prepare a 2% dodecylbenzenesulfonic acid aqueous solution. The aqueous solution was heated to 85 ℃, and the premixed organosiloxane latex was added dropwise over 4 hours, and after completion of the addition, the temperature was maintained for 1 hour and the mixture was cooled. After the reaction mixture was left at room temperature for 48 hours, it was neutralized with a sodium hydroxide solution to obtain a polyorganosiloxane latex (L-1). The solid content concentration of 17.3% was determined after drying a portion of the polysiloxane latex (L-1) at 170 ℃ for 30 minutes.

In a reactor including a reagent injection container, a cooling tube, a water jacket heating furnace, and a stirring device, 119.5 parts of polyorganosiloxane latex (L-1) and 0.8 part of sodium polyoxyethylene alkylphenyl ether sulfate were charged, and 203 parts of distilled water was added and mixed. Then, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1, 3-butanediol dimethacrylate and 0.13 part of tert-butyl hydroperoxide was added. The reactor was purged with nitrogen gas to replace the nitrogen atmosphere, and the temperature was raised to 60 ℃. When the internal temperature of the reactor reached 60 ℃, an aqueous solution in which 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetate, and 0.24 part of rongalite were dissolved in 10 parts of distilled water was added to start radical polymerization. The liquid temperature was raised to 78 ℃ by polymerization of the acrylate component. The reaction mixture was kept for 1 hour to complete the polymerization of the acrylate component, thereby obtaining a rubbery polymer (B1-4) latex composed of a composite rubber of polyorganosiloxane and butyl acrylate rubber.

After the temperature of the liquid in the reactor was decreased to 60 ℃, 10 parts of distilled water was added to dissolve 0.4 part of rongalite in water. Subsequently, a mixed liquid of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 part of t-butyl hydroperoxide was added dropwise over about 1 hour to polymerize the product. After the completion of the dropping, the mixture was kept for 1 hour, and then an aqueous solution prepared by dissolving 0.0002 part of ferrous sulfate, 0.0006 part of disodium ethylenediaminetetraacetate, and 0.25 part of rongalite in 10 parts of distilled water was added. Subsequently, a mixed liquid of 7.4 parts of acrylonitrile, 22.2 parts of styrene and 0.1 part of t-butyl hydroperoxide was added dropwise over about 40 minutes to polymerize the product. After the dropping was completed and the mixture was held for 1 hour, it was cooled to obtain a graft copolymer (B-4) latex in which an acrylonitrile-styrene copolymer was grafted to a rubbery polymer (B1-4) composed of a composite rubber of polyorganosiloxane and butyl acrylate rubber.

150 parts of an aqueous solution in which calcium acetate was dissolved in a proportion of 5% were heated to 60 ℃ and stirred. 100 parts of the graft copolymer (B-4) latex was slowly dropped in an aqueous calcium acetate solution, and allowed to coagulate. The obtained coagulated product was separated, washed and dried to obtain a dry powder of the graft copolymer (B-4).

The acetone-soluble portion of the graft copolymer (B-4) was 26%. And the reduced viscosity of the acetone-soluble portion was 0.6 dl/g.

[ inorganic Filler (D) ]

As the inorganic filler (D-1), a carbon fiber chopped strand (TR 06U manufactured by Mitsubishi Yang Co., Ltd., surface treatment agent: polyurethane) was used.

As the inorganic filler (D-2), chopped glass fiber (CSG 3PA-820 manufactured by Nidong textile Co., Ltd., surface treatment agent: polyurethane, ratio of long diameter/short diameter: 4) was used.

As the inorganic filler (D-3), chopped glass fiber (CSH 3PA-870 available from Nidong textile Co., Ltd., surface treatment agent: polyurethane, ratio of long diameter/short diameter: 2) was used.

As the inorganic filler (D-4), chopped glass fiber (CSH 3PA-850 manufactured by Nidong textile Co., Ltd., surface treatment agent: epoxy resin, ratio of long diameter/short diameter: 2) was used.

As the inorganic filler (D-5), chopped glass fibers (CS 3PE-455 manufactured by Nidong textile Co., Ltd., surface treatment agent: polyurethane, ratio of long diameter/short diameter: 1) were used.

[ glycidyl ether Unit-containing Polymer (E) ]

As the glycidyl ether unit-containing polymer (E-1), an epoxy group-containing phenoxy resin (manufactured by Mitsubishi chemical corporation, JER4250, mass average molecular weight: 60000) was used.

As the glycidyl ether unit-containing polymer (E-2), an epoxy group-containing phenoxy resin (manufactured by Mitsubishi chemical corporation, JER1256, mass average molecular weight: 50000) was used.

As the glycidyl ether unit-containing polymer (E-3), a bisphenol A type epoxy resin (manufactured by Mitsubishi chemical corporation, JER1010, mass average molecular weight: 5500) was used.

As the glycidyl ether unit-containing polymer (E-4), a bisphenol A type epoxy resin (manufactured by Mitsubishi chemical corporation, JER1009, mass average molecular weight: 3800) was used.

As the glycidyl ether unit-containing polymer (E-5), a bisphenol A type epoxy resin (manufactured by Mitsubishi chemical corporation, JER1004, mass average molecular weight: 1650) was used.

[ production of glycidyl Ether Unit-containing Polymer (E-6) ]

A separable flask having a capacity of 500ml and equipped with a stirrer, a thermometer, a nitrogen inlet and a cooling tube was charged with 82.42 parts of bisphenol A type epoxy resin (epoxy equivalent: 467G/eq), 6.3 parts of bisphenol A type liquid epoxy resin (epoxy equivalent: 210G/eq, hydrolyzable chlorine: 1.79%), 13.95 parts of bisphenol A, 19.6 parts of P-cumylphenol, 7.5 parts of polyester resin (manufactured by U-PICA, Japan, GV-335, acid value: 30KOHmg/G) and 30 parts of xylene, and heated under nitrogen atmosphere to raise the temperature. When the internal temperature of the reaction system reached 80 ℃, 0.18 part of 5% lithium chloride aqueous solution was added, and the temperature was further raised. When the internal temperature of the reaction system reached 130 ℃, xylene and water were taken out of the system by reducing the pressure in the reaction system. The reaction was carried out while maintaining the reaction temperature at 160 ℃ and, after one hour, nitrogen gas was introduced into the reaction system to return the internal pressure of the reaction system to normal pressure. Then, 20.25 parts of a high molecular weight bisphenol A type epoxy resin (epoxy equivalent: 2700g/eq) was added at a time of 7 hours from the time when the reaction temperature reached 160 ℃ and stirred for 1 hour, and then 100 parts of a polyester resin (GV-730, manufactured by U-PICA Co., Ltd., Japan, acid value: 3KOHmg/g) was added and reacted at 180 ℃ for 10 hours to obtain a high molecular weight epoxy resin. In order to provide the obtained high molecular weight epoxy resin for the measurement of molecular weight by GPC, about 0.05g was tried to be insoluble after dissolving a 0.1g sample in 10ml of tetrahydrofuran. After filtration through a 5C filter paper, the molecular weight of the filtrate was measured by GPC, and the mass average molecular weight was 70200.

[ Polyamide 6/66(F) ]

Polyamide 6/66(F-1) A polyamide 6/66 copolymer (5023B, relative viscosity: 3.0 and water content: 0.1%, available from Shikoku corporation) was used.

Polyamide 6/66(F-2) A polyamide 6/66 copolymer (5013B, relative viscosity: 2.5, water content: 0.1%, manufactured by Utsu corporation) was used.

Polyamide 6/66(F-3) A polyamide 6/66 copolymer (5023B, relative viscosity: 3.0 and water content: 0.2%, available from Shikoku corporation) was used.

Polyamide 66 (1500, manufactured by Asahi Kasei Kogyo Co., Ltd., relative viscosity: 3.7, water content: 0.1%) was used as the polyamide (F-4).

Polyamide (F-5) was polyamide 6 (1022B, relative viscosity: 3.4, water content: 0.1%, produced by Shikoku Kogyo Co., Ltd.).

Polyamide (F-6) used was polyamide 6 (1013B, relative viscosity: 2.6, water content: 0.1%) produced by Yu Shi Higheng Co., Ltd.

Incidentally, (F-1) is used immediately after the product bag is opened, and (F-3) is used after the product bag is opened for one week.

[ phosphoric acid ester flame retardant (G) ]

Bisphenol A bis (diphenyl phosphate) (BAPP, Mass average molecular weight: 692, catalog number) was used as the phosphate flame retardant (G-1).

As the phosphate flame retardant (G-2), phenylene bis (diphenyl) phosphate) (PX-200, Mass average molecular weight: 686, catalog number, available from Daxika chemical Co., Ltd.) was used.

As the phosphate flame retardant (G-3), phenylene bis (diphenyl phosphate) (manufactured by Dai eight chemical Co., Ltd., CR-733S, mass average molecular weight: 574, catalog number) was used.

Triphenyl phosphate (TPP, Mass average molecular weight: 326, catalog number) was used as the phosphate flame retardant (G-4).

[ flame retardant auxiliary (H) ]

Polytetrafluoroethylene (PTFE) was used as the flame retardant auxiliary (H-1).

< examples 1 to 32 and comparative examples 1 to 11>

The above components were mixed in the compositions shown in tables 1 to 7, and kneaded by using a twin-screw extruder to obtain pellets of the reinforced thermoplastic resin composition. The obtained pellets were dried at 100 ℃ for 3 hours, injection-molded and evaluated for moldability. The obtained molded article was measured for charpy impact strength, bending strength, flexural modulus, weld strength, heat resistance, and the like. The evaluation results are shown in tables 1 to 6.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

The amounts of the inorganic filler (D), the glycidyl ether unit-containing polymer (E), the polyamide 6/66(F), the phosphate flame retardant (G) and the flame retardant auxiliary (H) shown in tables 1 to 7 are the amounts (parts) based on 100 parts of the resin main component (C) comprising the polycarbonate resin (A) and the graft copolymer (B). The "proportion of D" shown in tables 1 to 7 is the proportion (%) of the inorganic filler (D) to the total mass (100 mass%) of the reinforced thermoplastic resin composition.

As shown in tables 1 to 5, the reinforced thermoplastic resin compositions obtained in the examples were excellent in moldability. Further, the reinforced thermoplastic resin compositions obtained in the examples can provide molded articles which are excellent in weld strength, rigidity, impact resistance, mechanical strength and heat resistance and in which warpage due to moisture absorption is suppressed.

On the other hand, as shown in tables 6 and 7, in comparative examples 1 to 11, the reinforced thermoplastic resin composition was inferior in any of moldability, weld strength of molded article, rigidity, impact resistance, mechanical strength and heat resistance.

Specifically, in comparative example 1 in which the proportion of the polycarbonate resin (a) was small and the proportion of the graft copolymer (B) was large, the impact resistance and weld strength were poor.

In comparative example 2 in which the proportion of the inorganic filler (D) was large, moldability was poor.

In comparative example 3 which does not contain the glycidyl ether unit-containing polymer (E), impact resistance and weld strength were poor.

In comparative example 4 containing no polyamide 6/66(F), the weld strength was poor.

In comparative example 5 in which the mass average molecular weight of the glycidyl ether unit-containing polymer (E) was 70200, moldability was poor.

In comparative example 6 in which the ratio of polyamide 6/66(F) was large, the weld strength was poor. And warpage due to moisture absorption occurs.

Comparative example 7, in which the mass average molecular weight of the polymer (E) containing glycidyl ether units was 1650, was inferior in impact resistance.

In comparative example 8 in which the polyamide 6/66(F) had a water content of 0.2%, the weld strength and heat resistance were poor.

In comparative examples 9 to 11 which contained polyamides other than polyamide 6/66(F), the weld strength was poor.

Further, it is understood from a comparison between example 8 and comparative example 3 that the reinforced thermoplastic resin composition of the present invention is superior in impact resistance, mechanical strength and weld strength when processed into a molded article, as compared with a reinforced thermoplastic resin composition containing no glycidyl ether unit-containing polymer (E).

As is clear from comparison between example 8 and comparative example 4, the reinforced thermoplastic resin composition of the present invention is superior in weld strength when processed into a molded article, as compared with a reinforced thermoplastic resin composition not containing polyamide 6/66(F) having a water content of 0.1% or less.

As is clear from comparison between example 8 and comparative example 8, the reinforced thermoplastic resin composition of the present invention is superior in weld strength and heat resistance when processed into a molded article, as compared with a reinforced thermoplastic resin composition containing polyamide 6/66(F) having a water content of more than 0.1%.

As is clear from comparison of example 8 and comparative examples 9 to 11, the reinforced thermoplastic resin composition of the present invention is superior in weld strength when processed into a molded article, as compared with a reinforced thermoplastic resin composition containing a polyamide other than polyamide 6/66 (F).

Industrial applicability

The reinforced thermal resin composition of the present invention is particularly useful as a material for a case of a mobile device (notebook and tablet personal computers, mobile phones including smart phones, digital cameras, digital video cameras, and the like).

Claims (7)

1. A reinforced thermoplastic resin composition, comprising:

a resin main component (C) comprising 80 to 95 mass% of a polycarbonate resin (A) and 0 to 50 mass% of a graft copolymer (B), wherein the total amount of the polycarbonate resin (A) and the graft copolymer (B) is 100 mass%, and the graft copolymer (B) is obtained by polymerizing a monomer mixture containing an aromatic alkenyl compound monomer (a) and a vinyl cyanide compound monomer (B) in the presence of a rubbery polymer (B1);

an inorganic filler (D);

the polymer (E) containing a glycidyl ether unit, excluding the graft copolymer (B), has a glycidyl ether unit and has a mass average molecular weight of 3800 to 60000; and

polyamide 6/66(F) having a water content of 0.1% or less,

the proportion of the inorganic filler (D) is 20 to 50 mass% with respect to 100 mass% of the total mass of the reinforced thermoplastic resin composition;

the content of the glycidyl ether unit-containing polymer (E) is 3 to 8 parts by mass per 100 parts by mass of the resin main component (C);

the polyamide 6/66(F) is contained in an amount of 5 to 10 parts by mass per 100 parts by mass of the resin main component (C).

2. The reinforced thermoplastic resin composition of claim 1, wherein the polyamide 6/66(F) has a relative viscosity of 1.5 to 4.5 as determined by an Ostwald viscometer using a 96 mass% sulfuric acid solution having a concentration of 1.0g/dl at 25 ℃.

3. The reinforced thermoplastic resin composition of claim 1 or 2, wherein the inorganic filler (D) is a carbon fiber.

4. The reinforced thermoplastic resin composition of claim 1 or 2, wherein the inorganic filler (D) is a glass fiber.

5. The reinforced thermoplastic resin composition of claim 1 or 2, wherein the reinforced thermoplastic resin composition further comprises a phosphate-based flame retardant (G).

6. The reinforced thermoplastic resin composition of claim 5, wherein the mass average molecular weight of the phosphate-based flame retardant (G) exceeds 326.

7. A molded article obtained by molding the reinforced thermoplastic resin composition according to claim 1 or 2.