HK1234765B

HK1234765B - Reinforced thermoplastic resin composition and molding

Info

Publication number: HK1234765B
Application number: HK17108611.3A
Authority: HK
Inventors: 中本正仁; 川口英一郎
Original assignee: Umg Abs株式会社
Priority date: 2014-07-03
Filing date: 2015-07-01
Publication date: 2019-01-04

Abstract

The present invention is a reinforced thermoplastic resin composition containing a main resin component (C) obtained from a polycarbonate resin (A) and a graft copolymer (B) as a discretionary component, an inorganic filler (D), a glycidyl ether unit-containing polymer (E) (excluding (B)) of 3,800 - 60,000 Mw, and a phosphorus-containing modified polyester resin (H) in which a phosphorus-containing polyester resin (F) has been modified with a polycarbodiimide compound (G). In the reinforced thermoplastic resin composition: (B) is a polymer obtained by polymerizing a monomer mixture comprising an aromatic alkenyl compound monomer (a) and a vinyl cyanide compound monomer (b) in the presence of a rubber polymer (B1); in (C), the contents of (A) and (B) are 80-100 mass% and 0-20 mass% respectively, and the total content of (A) and (B) is 100 mass%; (F) comprises the cyclic phosphorus compound-containing dicarboxylic acid component of formula (1); the phosphorus content is at least 4 mass%; the proportion of (D) is 20-50 mass% with respect to the reinforced thermoplastic resin composition; the content of (E) is 1-10 parts by mass with respect to 100 parts by mass of (C); and the content of (H) is 3-10 parts by mass with respect to 100 parts by mass of (C).

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 2014-137771 of japanese application No. 7/3 in 2014, the contents of which are incorporated herein by reference.

Background

As a housing material for notebook or tablet personal computers, mobile phones including smartphones, digital cameras, digital video cameras, and other mobile devices, thermoplastic resin compositions such as ABS resins, resins obtained by mixing polycarbonate resins and ABS resins (also referred to as polycarbonate resins/ABS resins), polyamide resins, mixed resins obtained by mixing polycarbonate resins and polyester resins (also referred to as polycarbonate resins/polyester resins), and the like, or these thermoplastic resin compositions reinforced with an inorganic filler have been 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 for a mobile 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 such as impact resistance, but also high weld strength, flame retardancy, and good moldability during molding when the composition is formed into a molded article.

However, thermoplastic resin compositions such as ABS resins, polycarbonate resins/ABS resins, polyamide resins, polycarbonate resins/polyester resins, which are not reinforced with inorganic fillers, have low rigidity when they are molded, and thus cannot satisfy the demand for making the housing thinner. Further, since polyamide resins have high moisture absorption, they tend to be warped, changed in size, deteriorated in appearance, and the like with the passage of time after being molded into a molded article.

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 the thermoplastic resin composition to improve rigidity has been studied.

However, although reinforced thermoplastic resin compositions containing ABS resin, polycarbonate resin/ABS resin, and polycarbonate resin/polyester resin as main components have high rigidity and can make the housing thin when formed into molded articles, they have insufficient weld strength and impact resistance when formed into molded articles.

In particular, a reinforced thermoplastic resin composition mainly composed of a polycarbonate resin/polyester resin is also poor in thermal stability. In addition, when the cylinder is kept at a high temperature in the molding step, decomposition gas is generated by the transesterification reaction between the polycarbonate resin and the polyester resin, and bubbles and appearance defects of the molded article called silver streaks are likely to occur. Further, the molecular weight of the polycarbonate resin is reduced by the transesterification reaction, and the impact resistance, heat resistance and the like inherent to the polycarbonate resin may be deteriorated. Further, the residence at high temperature causes a change in the viscosity of the polycarbonate resin, which impairs the molding stability during injection molding, and causes problems such as poor filling (also referred to as short shot) or excessive filling (also referred to as burr) of the obtained molded article.

On the other hand, a reinforced thermoplastic resin composition containing a polyamide resin as a main component is excellent in weld strength when molded articles are produced, but the problems of warpage, dimensional change, and poor appearance cannot be solved. This is because the molded article after molding absorbs moisture, and the problem cannot be solved even if the molding material is dried before molding.

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 a polycarbonate resin, a rubber-containing polymer, and carbon fibers bundled with a nylon-based bundling agent (patent document 3);

(4) a reinforced thermoplastic resin composition comprising a polycarbonate resin, a rubber polymer, polyethylene terephthalate which has been subjected to deactivation treatment of a polycondensation catalyst, milled fibers, and an olefin polymer having a functional group which reacts with the polycarbonate (patent document 4).

Documents of the prior art

Patent document 1: japanese laid-open patent publication No. 2013-14747

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

Patent document 3: japanese patent laid-open publication No. 60-88062

Patent document 4: japanese unexamined patent publication No. 2012-77241

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

(2) The reinforced thermoplastic resin composition of (1) has a problem that the mechanical strength other than the impact resistance, that is, the flexural strength and the tensile strength, is lowered when the composition is formed into a molded article.

(3) The reinforced thermoplastic resin composition of (1) has an excellent frequency of repeated impact when it is molded into a molded article, but has insufficient impact resistance.

(4) The reinforced thermoplastic resin composition of (1) has low rigidity when it is molded 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 balance among moldability, weld strength, mechanical strength, impact resistance and flame retardancy of the molded article obtained therefrom has been proposed.

Disclosure of Invention

The purpose of the present invention is to provide a reinforced thermoplastic resin composition having good moldability and giving a molded article having high weld strength, rigidity, impact resistance, mechanical strength, heat resistance or flame retardancy, and a molded article having high weld strength, rigidity, impact resistance, mechanical strength, heat resistance or flame retardancy.

The present invention includes the following modes.

[1] A reinforced thermoplastic resin composition comprising:

a resin main component (C) comprising 80 to 100 mass% of a polycarbonate resin (A) and 0 to 20 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

a phosphorus-containing modified polyester resin (H) obtained by modifying a polyester resin (F) containing phosphorus atoms with a polycarbodiimide compound (G),

the polyester resin (F) is produced by using a dicarboxylic acid component containing a cyclic phosphorus compound represented by the following formula (1) as a copolymer component, and the content of phosphorus atoms in 100 mass% of the polyester resin (F) is 4 mass% or more; the proportion of the inorganic filler (D) is 20 to 50 mass% in 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 content of the modified polyester resin (H) containing phosphorus is 3 to 10 parts by mass per 100 parts by mass of the resin main component (C).

[ chemical formula 1]

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

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

[4] The reinforced thermoplastic resin composition according to any one of [1] to [3], further comprising a phosphate flame retardant (I).

[5] A molded article obtained by molding the reinforced thermoplastic resin composition according to any one of [1] to [4 ].

<1> a reinforced thermoplastic resin composition comprising: a resin main component (C) composed of a polycarbonate resin (A) or composed of a polycarbonate resin (A) and a graft copolymer (B); 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 a phosphorus-containing modified polyester resin (H) obtained by modifying a polyester resin (F) containing a phosphorus atom with a polycarbodiimide compound (G), wherein the graft copolymer (B) is a polymer 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); in the resin main component (C), the content of the polycarbonate resin (A) is 80-100 mass%, the content of the graft copolymer (B) is 0-20 mass%, and the total content of the polycarbonate resin (A) and the graft copolymer (B) is 100%; the graft copolymer is a copolymer obtained by polymerizing a monomer mixture containing an aromatic vinyl compound monomer (a) and a vinyl cyanide compound monomer (B) in the presence of a rubbery polymer (B1); the polyester resin (F) contains a dicarboxylic acid component having a cyclic phosphorus compound represented by the following formula (1), and the content of phosphorus atoms in the polyester resin (F) is 4% by mass or more; the proportion of the inorganic filler (D) is 20 to 50 mass% relative to 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 content of the modified polyester resin (H) containing phosphorus is 3 to 10 parts by mass per 100 parts by mass of the resin main component (C).

[ chemical formula 2]

Advantageous effects

The reinforced thermoplastic resin composition of the present invention has good moldability, and can improve weld strength, rigidity, impact resistance, mechanical strength, heat resistance or flame retardancy of the resulting molded article.

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

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), an inorganic filler (D), a polymer (E) containing a glycidyl ether unit, and a modified polyester-based resin (H) containing phosphorus. The resin main component (C) contains the polycarbonate resin (a) shown below, and may further contain a graft copolymer (B). Further, preferably, the reinforced thermoplastic resin composition further comprises a phosphate flame retardant (I), a flame retardant aid (J).

[ resin Main component (C) ]

The resin main component (C) contains a polycarbonate resin (A), or a polycarbonate resin (A) and a graft copolymer (B). That is, the resin main component (C) may or may not contain the graft copolymer (B).

The proportion of the resin main component (C) is preferably 35 to 75% by mass relative to the total mass of the reinforced thermoplastic resin composition.

In the main resin component (C), the proportion of the polycarbonate resin (A) is 80 to 100% by mass, preferably 90 to 95% by mass, based on the total mass of the main resin component (C). When the proportion of the polycarbonate resin (A) is within the above range, the moldability of the reinforced thermoplastic resin composition is good. In particular, when the proportion of the polycarbonate resin (A) is 80% by mass or more, the flame retardancy, mechanical strength and rigidity of the molded article are improved; when the content is 95% by mass or less, the moldability of the reinforced thermoplastic resin composition is further improved.

In the main resin component (C), the proportion of the graft copolymer (B) is 0 to 20% by mass, preferably 5 to 10% by mass, based on the total mass of the main resin component (C). When the proportion of the graft copolymer (B) is within the above range, the moldability of the reinforced thermoplastic resin composition is good. In particular, when the proportion of the graft copolymer (B) is 20% by mass or less, the flame retardancy, mechanical strength and rigidity of the molded article are improved; when the content is 5% by mass or less, the moldability of the reinforced thermoplastic resin composition is further improved.

The total of the proportions of the polycarbonate resin (a) and the graft copolymer (B) in the resin main component (C) is 100% by mass.

< polycarbonate resin (A) >

The polycarbonate resin (a) is a resin obtained from a bis (hydroxyaryl) hydrocarbon. The polycarbonate resin (a) may be unbranched or branched.

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 unbranched polycarbonate resin (a) is produced by a method of reacting a bis (hydroxyaryl) hydrocarbon with phosgene or a diester of carbonic acid, or a melt polymerization method.

Examples of the bis (hydroxyaryl) hydrocarbon include bis (hydroxyaryl) hydrocarbons having an alkyl group at the ortho-position with respect to the hydroxyl group in the hydroxyaryl structure.

Preferred specific examples of the bis (hydroxyaryl) hydrocarbon include: 4,4 '-dihydroxy-2, 2' -diphenylpropane (i.e., bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) p-diisopropylbenzene, and the like.

The branched polycarbonate resin (a) is produced by a method in which a compound having a structure in which three or more hydroxy groups such as bis (hydroxyaryl) hydrocarbon and poly (hydroxyaryl) hydrocarbon are bonded to benzene rings is reacted with phosgene or a diester of carbonic acid, or a melt polymerization method. For example, the branched polycarbonate resin (A) is produced by using 98 to 99.8 mol% of a bis (hydroxyaryl) hydrocarbon and 0.2 to 2 mol% of a poly (hydroxyaryl) hydrocarbon, relative to the total amount of compounds having a structure in which three or more bis (hydroxyaryl) hydrocarbons and a hydroxyl group are bonded to a benzene ring. Specific examples of the compound having a structure in which three or more hydroxy groups such as poly (hydroxyaryl) hydrocarbon are bonded to a benzene ring include: 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, for example, a solution viscosity method. When a commercially available polycarbonate resin (A) is used, the catalog value may be referred to.

< 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).

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 satisfactory flame retardancy of the molded article, a silicone-acrylic composite rubber is preferable.

In the present invention, the composite rubber means, for example, a rubber obtained by copolymerizing two rubber components or a rubber polymerized so as to be complexed with each other and not to be separated and to have an IPN structure.

(butadiene rubber)

The butadiene rubber is preferably such that the proportion of the butadiene monomer is 95 to 100% by mass based on the total mass of the monomers forming the butadiene rubber. As further monomers, butadiene rubbers may comprise alkyl (meth) acrylates, such as n-butyl acrylate or methacrylate.

(acrylic rubber)

The acrylic rubber is preferably such that the proportion of the alkyl (meth) acrylate is 95 to 100% by mass based on the total mass of the monomers forming the acrylic rubber.

(diene-acrylic acid compounded rubber)

The diene component in the diene-acrylic composite rubber preferably includes 50% by mass or more and less than 100% by mass of a butadiene unit, and more preferably 95% by mass or more and 99% by mass or less, relative to the total mass of the monomers forming the diene component of the diene-acrylic composite rubber. Examples of the diene component include: butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and 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 such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate. 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, 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. In the present invention, the polyorganosiloxane is a polymer formed by alternately bonding silicon and oxygen, and means a silicon-bonded organic group. 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.

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

The polymerization rate of the rubbery polymer (B1) is preferably 85 to 99%. The polymerization rate can be calculated from the change in the amount of the rubbery polymer produced by the reaction by measuring the amount of the unreacted monomer.

The average particle diameter is a value measured by a dynamic light scattering method.

(content of rubbery Polymer (B1))

The content of the rubbery polymer (B1) is preferably 0.5 to 3.5% by mass based on the total mass (100% by mass) of the resin main component (C). 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.

(Mass average molecular weight of the rubbery Polymer (B1))

The mass average molecular weight of the rubbery polymer (B1) is preferably 20000 to 200000, more preferably 40000 to 150000.

The mass average molecular weight of the rubbery polymer (B1) can be determined by, for example, Gel Permeation Chromatography (GPC).

[ 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 each monomer unit is preferably 50 to 90% by mass of the aromatic alkenyl compound monomer (a) unit, 10 to 50% by mass of the vinyl cyanide compound monomer (B) unit, and 0 to 40% by mass of the other monomer (c) unit, based on the total mass of the monomers forming the molecular chain (B2). Further, the molecular chain (B2) more preferably contains 60 to 80 mass% of the aromatic vinyl compound monomer (a) unit and 20 to 40 mass% of the vinyl cyanide compound monomer (B) unit, and does not contain other monomer (c) unit. However, 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, with styrene being preferred.

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

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

[ Mass average molecular weight of graft copolymer (B) ]

The graft copolymer (B) preferably has a mass average molecular weight of 35000 to 600000, more preferably 55000 to 500000, 100000 to 450000.

Further, the mass average molecular weight of the graft copolymer (B) defined herein means the molecular weight of the polymer contained in the acetone-soluble portion. The mass average molecular weight can be measured by dissolving an acetone-soluble fraction in tetrahydrofuran, measuring by Gel Permeation Chromatography (GPC), and calculating the mass average molecular weight (Mw) in terms of polystyrene.

The graft copolymer (B) is a copolymer comprising an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit as essential components in a rubbery polymer (B1) and bonding a molecular chain (B2) as a graft chain, wherein the molecular chain (B2) contains, as an optional component, another monomer (c) unit copolymerizable with the aromatic alkenyl compound monomer (a) unit and the vinyl cyanide compound monomer (B) unit, and the graft copolymer (B) is composed of a core part composed of the composite rubbery polymer (a) and an outer layer part composed of the molecular chain (B2).

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

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

< 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, a titanate coupling agent, etc.) 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 urethane resin or an epoxy resin.

The ratio of the major diameter to the minor diameter (hereinafter also referred to as major diameter/minor diameter) in the fiber cross section of the glass fiber or the carbon fiber is preferably 2 to 6, and more preferably 2 to 4. When the major/minor diameter is 2 or more, good impact resistance and strength are obtained. When the major/minor diameter is 6 or less, good moldability, that is, extrusion workability is obtained. In addition, the long diameter is preferably 7 to 28 nm.

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 product catalog value can be referred to.

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 preferably 20 to 50% by mass, more preferably 30 to 45% by mass, based on the total 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 block-type polymer having a halogen atom such as bromine.

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 3]

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 phenol novolak type epoxy resins and cresol novolak type epoxy resins.

Examples of the polyglycidyl ethers of aliphatic polyhydric alcohols include: alkylene glycol diglycidyl ethers such as ethylene glycol diglycidyl ether; polyoxyalkylene glycol diglycidyl ethers such as diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; 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, or an epoxy group-containing phenoxy resin, from the viewpoint of further improving the mechanical strength of the molded article. The glycidyl ether unit-containing polymer (E) is more preferably a bisphenol a type epoxy resin or an epoxy group-containing phenoxy resin.

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

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 of the molded article is improved. When the mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 60000 or less, the moldability of the reinforced thermoplastic resin composition and the flame retardancy of the molded article are good.

The mass average molecular weight of the glycidyl ether unit-containing polymer (E) can be determined by mass analysis. When a commercially available polymer (E) containing glycidyl ether units is used, reference is made to the catalog values.

[ 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, the 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, the moldability of the reinforced thermoplastic resin composition and the flame retardancy of the molded article are good.

< modified polyester resin containing phosphorus (H) >

The phosphorus-containing modified polyester resin (H) is obtained by modifying a polyester resin (F) containing phosphorus atoms with a polycarbodiimide compound (G).

The phosphorus-containing modified polyester resin (H) may be used alone or in combination of two or more.

[ polyester resin (F) ]

The polyester-based resin (F) contains phosphorus atoms and mainly functions as a flame retardant. The content of phosphorus atoms in the polyester resin (F) is 4% by mass or more. When the content of the phosphorus atom is 4% by mass or more, the effect of improving the flame retardancy of the polyester resin (F) can be sufficiently obtained. From the viewpoint of industrial mass production, the content of phosphorus atoms is preferably 6 mass% or less, and more preferably 4 mass% or more and 6 mass% or less.

The polyester resin (F) is produced by using a dicarboxylic acid component containing a cyclic phosphorus compound represented by the following formula (1) as a copolymer component.

[ chemical formula 4]

The cyclic phosphorus compound represented by the above formula (1) can be produced by an addition reaction of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter, sometimes abbreviated as "DOP") represented by the following formula (3) and itaconic acid represented by the following formula (4). The addition reaction may occur during the polyester manufacturing process.

Therefore, the polyester-based resin (F) can be produced by a polycondensation reaction according to a usual method using a polyester production raw material (copolymerization component) containing DOP, itaconic acid, other dicarboxylic acid component and a diol component, as described in international publication No. 2006/057228.

[ chemical formula 5]

In particular, the polyester-based resin (F) is preferably a product obtained by reacting a dicarboxylic acid component and a diol component, wherein the dicarboxylic acid component comprises terephthalic acid and/or an ester-forming derivative thereof (e.g., dimethyl terephthalate), a cyclic phosphorus compound represented by the above formula (1), and a trifunctional or higher polycarboxylic acid component.

The proportion of terephthalic acid and/or its ester-forming derivative is preferably 49.5 mol% or more, more preferably 55 to 69.5 mol% with respect to the total amount of dicarboxylic acid components used in the reaction.

The proportion of the cyclic phosphorus compound represented by the above formula (1) is preferably 29.5 mol% or more, and more preferably 30 to 49.5 mol% with respect to the total amount of the dicarboxylic acid component used for the reaction.

The proportion of the trifunctional or higher polycarboxylic acid component is preferably 0.05 to 2.0 mol%, more preferably 0.30 to 0.70 mol%, based on the total amount of the dicarboxylic acid component used in the reaction.

However, the total of the terephthalic acid and/or its ester-forming derivative, the cyclic phosphorus compound represented by the formula (1), and the trifunctional or higher polycarboxylic acid component is 100 mol%.

When the ratio of terephthalic acid and/or an ester-forming derivative thereof is not less than the lower limit, the material itself is less likely to become brittle and the productivity is good, so that the industrial mass production is possible.

On the other hand, when the ratio of terephthalic acid and/or an ester-forming derivative thereof is not more than the above upper limit, the ratio of the cyclic phosphorus compound represented by the above formula (1) to the trifunctional or higher polycarboxylic acid component can be secured, and therefore the effects of these components can be sufficiently obtained.

When the proportion of the cyclic phosphorus compound represented by the above formula (1) is within the above range, the phosphorus atom content of the polyester-based resin (F) obtained can be easily made within the above range.

The trifunctional or higher polycarboxylic acid component is used for accelerating the polymerization reaction using the cyclic phosphorus compound represented by the above formula (1) because of its thickening effect, and when the proportion is not less than the above lower limit, the thickening effect is sufficiently obtained; if the upper limit value is less than the upper limit value, the polymerization reaction can be easily controlled.

Examples of the trifunctional or higher polycarboxylic acid component include trimellitic acid, ethane tricarboxylic acid, propane tricarboxylic acid, butane tetracarboxylic acid, pyromellitic acid, trimesic acid, 3,4,3 ', 4' -biphenyl tetracarboxylic acid, and ester-forming derivatives thereof.

On the other hand, examples of the ethanol component include ethylene glycol and ethylene oxide.

As the raw material for producing the polyester-based resin (F), other dicarboxylic acid components than those described above, trifunctional or higher polyvalent polyol components, and the like can be used.

The polyester resin (F) preferably has an intrinsic viscosity of 0.4 to 0.7dl/g from the viewpoints of flame retardancy, impact resistance and heat resistance of the molded article. When the polymers of the same kind are used in the same solvent and at the same temperature, the higher the intrinsic viscosity, the higher the molecular weight. When the intrinsic viscosity is less than the above range, appearance defects, impact resistance and heat resistance of the molded article may be deteriorated, and when the intrinsic viscosity is more than the above range, flame retardancy may be deteriorated.

As the polyester resin (F), commercially available products such as "Byron GH 250" manufactured by Toyo Boseki can be used.

[ polycarbodiimide Compound (G) ]

In the present specification, the polycarbodiimide compound (G) is a compound having one or more carbodiimide groups, i.e., groups represented by-N ═ C ═ N-in one molecule. The polycarbodiimide compound may be any one known in the art, and is not particularly limited.

Examples of the polycarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, octyldecylcarbodiimide, di-t-butylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, N-octadecyl-N '-phenylcarbodiimide, N-benzyl-N' -tolylcarbodiimide, di-o-tolylcarbodiimide, di-p-tolylcarbodiimide, bis (p-aminophenyl) carbodiimide, bis (p-chlorophenyl) carbodiimide, bis (o-ethylphenyl) carbodiimide, bis (p-ethylphenyl) carbodiimide, bis (o-isopropylphenyl) carbodiimide, bis (p-isopropylphenyl) carbodiimide, bis (o-isobutylphenyl) carbodiimide, bis (p-isobutylphenyl) carbodiimide, bis (2, 5-dichlorophenyl) carbodiimide, bis (2, 6-dimethylphenyl) carbodiimide, bis (p-isopropylphenyl) carbodiimide, bis (o-isobutylphenyl) carbodiimide, bis (p-isopropylphenyl) carbodiimide, bis (2, 6-di-t-butylphenyl) carbodiimide, bis (p-butylphenyl) carbodiimide, bis (o-isopropylphenyl) carbodiimide, bis (p-butylphenyl) carbodiimide, bis (4, 6-di-t-butylphenyl) carbodiimide, bis (o-butylphenyl) carbodiimide, bis (p-isopropylphenyl) carbodiimide, bis (2, 6-isopropylphenyl) carbodiimide, bis (p-isopropylphenyl) carbodiimide, bis (2, 6-isopropylphenyl) carbodiimide, bis (4, 6-di-6-isopropylphenyl) carbodiimide, bis (p-cyclohexylene, bis (2, bis (4-isopropylphenyl) carbodiimide, 6-di-isopropylphenyl) carbodiimide, bis (2, 6-di-6-di-isopropylphenyl) carbodiimide, bis (4, bis (p-6-di-cyclohexylene) carbodiimide, bis (2, bis (p-di-butyl) carbodiimide, bis (p-butyl) carbodiimide, bis (2, bis (4, bis (2, 6-butyl) carbodiimide, bis (2, bis.

Among these, bis (2, 6-diisopropylphenyl) carbodiimide and 2,6,2 ', 6' -tetraisopropyldiphenylcarbodiimide are preferable from the viewpoint of reactivity and stability.

The polycarbodiimide compound (G) may be commercially available, for example, commercially available from Nisshinbo chemical company, sold under the trade name "Carbodilite".

[ Process for producing modified polyester-based resin (H) containing phosphorus ]

The phosphorus-containing modified polyester resin (H) is obtained by modifying the polyester resin (F) with a polycarbodiimide compound (G). That is, the modified polyester-based resin (H) containing phosphorus has a carboxyl group of the polyester-based resin (F) and a polycarbodiimide compound (R)⁵-N＝C＝N-R⁶) HR of carbodiimide group reaction⁶NCONR⁵Structure of OC-. Wherein R is⁵、R⁶Respectively, a hydrogen atom or an organic group.

The phosphorus-containing modified polyester resin (H) is 2200 to 2300cm in infrared absorption analysis^-1Has a characteristic peak value not recognized in the polyester-based resin (F) and the polycarbodiimide compound (G).

The modification method may be any method known in the art, and examples thereof include a method of kneading the polyester-based resin (F) and the polycarbodiimide compound (G) using a twin-screw extruder. The compounding ratio of the polycarbodiimide compound (G) is preferably 0.2 to 1 part by mass, more preferably 0.5 to 0.8 part by mass, relative to 100 parts by mass of the polyester-based resin (F). When the blending amount of the polycarbodiimide compound (G) to the polyester-based resin (F) is 0.2 parts by mass or more, the polyester-based resin (F) is sufficiently modified to improve the weld strength; when the amount is 1.0 part by mass or less, the unmodified polycarbodiimide compound (G) is less likely to remain, and good impact resistance can be maintained.

[ content of phosphorus-containing modified polyester-based resin (H) ]

The content of the phosphorus-containing modified polyester resin (H) is 3 to 10 parts by mass, preferably 5 to 8 parts by mass, per 100 parts by mass of the resin main component (C). When the content of the phosphorus-containing modified polyester-based resin (H) is 3 parts by mass or more, the weld strength of the molded article is improved. When the content of the phosphorus-containing modified polyester-based resin (H) is 10 parts by mass or less, the flame retardancy of the molded article is good. Also, a decrease in welding strength 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 (I) and a known non-halogen flame retardant.

[ phosphoric acid ester flame retardant (I) ]

The phosphoric ester flame retardant (I) may be a compound represented by the following formula (5).

[ chemical formula 6]

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.

Examples of the organic group include a substitutable alkyl group such as a methyl group, an ethyl group, a butyl group, and an octyl group; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and alkyl-substituted phenyl. The number of substituents in substitution is not particularly limited as long as it is chemically allowable. Examples of the substituted organic group include an alkoxy group, an alkylthio group, an aryloxy group, and an arylthio group. 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, phenylene, and substituted phenylene. 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 (I) 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 esters (bisphenol a diphosphate, hydroquinone diphosphate, resorcinol diphosphate, trisphenol triphosphate, bisphenol a bis (xylylphosphate), bisphenol a bis (diphenyl phosphate), phenylene bis (xylylphosphate), phenylene bis (dixylylphosphate), and the like) and the like.

The phosphate flame retardant (I) 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 (I))

The mass average molecular weight of the phosphate flame retardant (I) is preferably 326 or more, more preferably 326 or more, and particularly preferably 550 or more. When the phosphate flame retardant (I) 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 (I) 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 (I) is preferably 326 or more and 692 or less, more preferably 326 or more and 690 or less, and particularly preferably 550 or more and 686 or less.

The mass average molecular weight of the phosphate flame retardant (I) can be obtained by mass analysis. When a commercially available phosphate flame retardant (I) is used, the catalog value can be referred to.

(method for obtaining phosphate flame retardant (I))

Examples of commercially available phosphate flame retardants (I) 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 (I))

The content of the phosphate flame retardant (I) 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 (I) is 1 part by mass or more, the moldability of the molded article is further improved. When the content of the phosphate flame retardant (I) is 25 parts by mass or less, the impact resistance and heat resistance of the molded article are 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 (J) >

The reinforced thermoplastic resin composition of the present invention may contain a flame retardant aid (J) for preventing dripping during burning. Examples of the flame retardant aid (J) 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 (J), the content of the flame-retardant auxiliary (J) is preferably 1 part by mass or less, more preferably 0.1 part by mass or more and 1 part by mass or less, per 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 resin main component (C), an inorganic filler (D), a polymer (E) containing a glycidyl ether unit, and a modified polyester-based resin (H) containing phosphorus. The reinforced thermoplastic resin composition of the present invention may further contain a flame retardant, a flame retardant aid (J), and other components, as required.

Specifically, when the above components are mixed, the components are mixed using a mixing device such as a henschel mixer, a tumbler mixer, or a nauta mixer. Further, a kneading apparatus such as a single screw extruder, a twin screw extruder, a banbury mixer, or a co-kneader may be used for kneading.

< Effect >

The reinforced thermoplastic resin composition of the present invention described above contains the resin main component (C), the inorganic filler (D), the glycidyl ether unit-containing polymer (E), and the phosphorus-containing modified polyester-based resin (H) in a specific ratio, and therefore, has good moldability, and can improve the weld strength, rigidity, impact resistance, mechanical strength, heat resistance, or flame retardancy of the resulting molded article. The molded article preferably has good weld strength, rigidity, impact resistance, mechanical strength, heat resistance, and flame retardancy.

[ 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 a film, a glass plate, or the like, injection compression molding, extrusion, blow molding, vacuum molding, pressure molding, calendering, inflation molding, and the like. Among them, injection molding and injection compression molding are preferable because a molded product having excellent mass productivity and high dimensional accuracy can be obtained.

The welding strength of the molded product is a force when a crack is generated by pressing a welding point of the molded product with a terminal at one point. The test piece was a 1mm thick plate of a4 size. The weld strength of the molded article is preferably 120N or more, more preferably 130N or more, and particularly preferably 150N or more. The welding points are formed by joining resins in a mold having a size of a4 by providing a plurality of molten resin injection ports in the mold. The mold used was one having a molten resin inlet at the center of the mold, two positions 40mm from the short side of the rectangle A4 and 35mm from the long side, and two positions 40mm from the short side of the rectangle A4 and 25mm from the long side.

The rigidity of the molded article can be evaluated by the flexural modulus of elasticity measured in accordance with ISO178 of the molded article. The thickness, width and length of the test piece were 4mm, 10mm and 80mm, respectively. The flexural modulus of the molded article is preferably 6500MPa or more, more preferably 10000MPa or more, and still more preferably 13000MPa or more. The flexural modulus is preferably as high as possible, but is, for example, 17000MPa or less.

The impact resistance of the molded article can be evaluated by the Charpy impact strength measured in accordance with ISO179 of the molded article. Thickness of test pieceThe degree, the width and the length are respectively 4mm, 10mm and 80 mm. The Charpy impact strength of the molded article is preferably 10kJ/m²Above, more preferably 12kJ/m²Above, it is more preferably 15kJ/m²The above. The Charpy impact strength is preferably as high as possible, but is, for example, 30kJ/m²The following.

The mechanical strength of the molded article can be evaluated by the bending strength measured in accordance with ISO178 of the molded article. The thickness, width and length of the test piece were 4mm, 10mm and 80mm, respectively. The bending strength of the molded article is preferably 150MPa or more, more preferably 180MPa or more, and still more preferably 200MPa or more. The higher the flexural strength, the better, but it is, for example, 300MPa or less.

The heat resistance of the molded article can be evaluated by the flexural temperature measured according to ISO75 of the molded article and the 1.80MPa flat pressing method. The deflection temperature of the molded article is preferably 90 ℃ or higher, more preferably 100 ℃ or higher, and still more preferably 120 ℃ or higher. The higher the deflection temperature, the better, but for example, 150 ℃ or lower.

The flame retardancy of the molded article can be evaluated by determining whether it is equivalent to V-1 according to UL 94. The thickness of the test piece was 1 mm. The flame retardancy of the molded article is preferably comparable to that of V-1.

The test pieces used for the above measurement were all prepared by molding the composition with an injection molding machine at a molding temperature of 280 to 320 ℃.

That is, one aspect of the present invention is a reinforced thermoplastic resin composition which shows the weld strength, rigidity, impact resistance, mechanical strength, heat resistance or flame retardancy when the test piece is prepared by injection molding the composition of the present invention at a molding temperature of 280 to 320 ℃.

The molded article of the present invention can be suitably used for personal computers including notebook and tablet computers, projectors including liquid crystal projectors, televisions, printers, facsimiles, copiers, audio devices, game machines, cameras including video cameras and digital cameras, video devices including video recorders, mobile devices such as musical instruments, electronic notebooks and Personal Digital Assistants (PDAs), lighting devices, housings of communication devices including mobile phones and smartphone phones, game machine devices such as fishing tackle and pachinko products, vehicle products, furniture products, sanitary products, building material products, and the like. Among these applications, the present invention is particularly effective and suitable for a case of a mobile device such as a personal computer including a notebook and a tablet, a portable device including a smartphone, and the like.

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 90 ℃. 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 cover (thickness 1mm) of a notebook personal computer of a size of a4 was molded by the same molding method as in the evaluation of the welding strength. Moldability was evaluated based on whether there was short shot (unfilled portion) at the time of molding and whether sink marks and gas scorch occurred.

◎ no unfilled, sink marks, gas scorched.

○ sink marks were partially found.

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

[ flame retardancy ]

A test piece (width 12.7mm, length 127mm, thickness 1.0mm) was produced by molding the reinforced thermoplastic resin composition, and its flame retardancy was evaluated in accordance with UL94 as follows.

The lower end of the above test piece, which was vertically supported, was held for 10 minutes for the burner flame, and then the burner flame was removed from the test piece. After the flame disappeared, the same operation was carried out again with the burner flame. Thereafter, whether or not the flame-retardant property is equivalent to V-1 in UL94 was judged by the presence or absence of flame combustion duration after the first contact flame was completed, the sum of the 2 nd flame combustion duration and the flameless combustion duration, and the presence or absence of combustion droppings, and the flame-retardant property was evaluated according to the following evaluation criteria. The V-1 standard is "the first flaming combustion duration exceeds 10 seconds and is within 30 seconds, and the sum of the second flaming combustion duration and the flameless combustion duration exceeds 30 seconds and is within 60 seconds, and there is no combustion debris".

○ flame retardancy of V-1 class.

X: does not have V-1 rating for flame retardancy.

< 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 of 35% and an average particle diameter of 0.08 μm (solid content: 100 parts) was added a copolymer latex having an 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) with stirring. Stirring was continued for 30 minutes to obtain an enlarged butadiene rubbery polymer latex (B1-1) having an 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. The temperature was raised while stirring, and at a time point of internal temperature 60 ℃, 0.1 part of ferrous sulfate, 0.4 part of sodium pyrophosphate, and 0.06 part of sodium hydrosulfite were added, and then a mixture comprising 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 polymerization rate was 98%.

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 a nitrogen atmosphere for polymerization to obtain a rubbery polymer (B1-2) latex. The average particle size was 0.29. mu.m.

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) of 29/71, and after nitrogen substitution, the monomer mixture was fed at a rate of 30 parts/hr by a metering pump into a reactor containing the latex of the rubbery polymer (B1-2). 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 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. After cooling, the resulting mixture was dewatered 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 0.70 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 of 35% and an 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. Stirring was continued for 30 minutes to obtain an enlarged diene rubber latex having an 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 average particle size was 0.32. mu.m.

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 to a reactor containing the latex of the rubbery polymer (B1-3) through a metering pump at a rate of 15 parts/hr. 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 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. After cooling, the resulting mixture was dewatered 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 0.70 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 in a high-speed stirrer at 10000 rpm, 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. The average particle size was 0.12. mu.m.

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 0.60 dl/g.

[ inorganic Filler (D) ]

As the inorganic filler (D-1), a carbon fiber chopped fiber (TR 06U manufactured by Mitsubishi Yang, surface treatment agent: polyurethane, ratio of long diameter/short diameter: 1/1) 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 fiber (CSH 3PE-455 manufactured by Nidong textile Co., Ltd., surface treatment agent: polyurethane, ratio of long diameter/short diameter: 1) was 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. At a time of 7 hours from the time when the reaction temperature reached 160 ℃, 20.25 parts of a high molecular weight bisphenol A type epoxy resin (epoxy equivalent: 2700g/eq) was added, and after stirring for 1 hour, 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.

[ production of modified polyester resin containing phosphorus (H-1) ]

100 parts of Byron GH250 (manufactured by Toyo Boseki Co., Ltd., phosphorus atom content: 5%, intrinsic viscosity 0.52dl/G) as an unmodified polyester-based resin (F-1) containing phosphorus atoms and 0.5 part of Carbodilite HMV-8CA (manufactured by Nisshinbo Co., Ltd.) as a polycarbodiimide compound (G-1) were kneaded by a twin-screw extruder to obtain a phosphorus-containing modified polyester-based resin (H-1) in which the polyester-based resin (F-1) was modified with the polycarbodiimide compound (G-1).

[ production of modified polyester resin containing phosphorus (H-2) ]

100 parts of Byron GH230 (manufactured by Toyo Boseki Co., Ltd., phosphorus atom content: 3%) as an unmodified polyester-based resin (F-2) containing phosphorus atoms and 0.5 part of Carbodilite HMV-8CA (manufactured by Nisshinbo Co., Ltd., phosphorus atom content: 3%) as a polycarbodiimide compound (G-1) were kneaded by a twin-screw extruder to obtain a phosphorus-containing modified polyester-based resin (H-2) in which the polyester-based resin (F-2) was modified with the polycarbodiimide compound (G-1).

[ production of modified polyester resin (H-3) containing no phosphorus ]

100 parts of Novapex GM502S (manufactured by Mitsubishi chemical Co., Ltd., phosphorus atom content: 0%) as an unmodified polyester-based resin (F-3) not containing phosphorus atoms and 0.5 part of Carbodilite HMV-8CA (manufactured by Nisshinbo chemical Co., Ltd.) as a polycarbodiimide compound (G-1) were kneaded using a twin-screw extruder to obtain a phosphorus-containing modified polyester-based resin (H-3) in which the polyester-based resin (F-3) was modified with the polycarbodiimide compound (G-1).

[ production of phosphorus-containing unmodified polyester resin (H-4) ]

As the phosphorus-containing unmodified polyester-based resin (H-4), an unmodified polyester-based resin (F-1) containing a phosphorus atom (manufactured by Toyo Boseki Co., Ltd. "Byron GH 250", phosphorus atom content: 5%, intrinsic viscosity: 0.52dl/g) was used.

[ phosphoric acid ester flame retardant (I) ]

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

As the phosphate flame retardant (I-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 (I-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, available from Dai chemical Co., Ltd.) was used as the phosphate flame retardant (I-4).

[ flame retardant auxiliary (J) ]

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

< examples 1 to 30 and comparative examples 1 to 11>

The above components were mixed as shown in tables 1 to 6, and kneaded 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 flame retardancy. The evaluation results are shown in tables 1 to 6.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

The amounts of the inorganic filler (D), the glycidyl ether unit-containing polymer (E), the phosphorus-containing modified polyester resin (H) and its substitute, the phosphate flame retardant (I), and the flame retardant auxiliary (J) in tables 1 to 6 are amounts (parts) based on 100 parts of the resin main component (C). Further, the "proportion of C" and the "proportion of D" are the proportions (%) of the resin main component (C) and the inorganic filler (D) in 100% of the reinforced thermoplastic resin composition, respectively.

As shown in tables 1 to 6, the reinforced thermoplastic resin compositions obtained in the examples were excellent in moldability. Further, the reinforced thermoplastic resin compositions obtained in the examples can give molded articles excellent in weld strength, rigidity, impact resistance, mechanical strength, heat resistance and flame retardancy.

On the other hand, in comparative examples 1 to 11, the reinforced thermoplastic resin composition is inferior to the examples in any of moldability, weld strength, rigidity, impact resistance, mechanical strength, heat resistance and flame retardancy of the molded article.

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 rigidity, mechanical strength and flame retardancy 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 phosphorus-containing modified polyester-based resin (H), the weld strength was poor.

The glycidyl ether unit-containing polymer (E) had a mass average molecular weight of 70200 and a content of 12 parts per 100 parts of the resin main component (C), and was inferior in moldability and flame retardancy in comparative example 5.

In comparative example 6 in which the proportion of the phosphorus-containing modified polyester-based resin (H) was large, the weld strength and flame retardancy were poor.

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 proportion of the phosphorus-containing modified polyester-based resin (H) was small, the weld strength was poor.

In comparative examples 9 and 10 in which the content of phosphorus atoms in the polyester resin (F) was less than 4% by mass, the flame retardancy was poor.

In comparative example 11 in which the polyester-based resin (F) containing phosphorus atoms was not modified, 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 and weld strength when formed into a molded article, as compared with a reinforced thermoplastic resin composition not containing the glycidyl ether unit-containing polymer (E).

From the comparison between example 8 and comparative example 4, it is understood that the reinforced thermoplastic resin composition of the present invention is superior in weld strength when formed into a molded article, as compared with a reinforced thermoplastic resin composition containing no modified polyester resin (H) containing phosphorus.

As is clear from comparison between example 8 and comparative examples 9 and 10, the reinforced thermoplastic resin composition of the present invention is superior in flame retardancy when it is used to produce a molded article, as compared with a reinforced thermoplastic resin composition containing a modified polyester-based resin (H-2) containing phosphorus or a modified polyester-based resin (H-3) containing no phosphorus, the modified polyester-based resin (F) containing less than 4 mass% of phosphorus atoms.

From the comparison between example 8 and comparative example 11, it is understood that the reinforced thermoplastic resin composition of the present invention is superior in weld strength when it is formed into a molded article, as compared with a reinforced thermoplastic resin composition containing a phosphorus-containing modified polyester-based resin (H-4) in which the polyester-based resin (F) having a phosphorus atom content of 4 mass% or more is not modified.

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

1. A reinforced thermoplastic resin composition, comprising:

a resin main component (C) composed of a polycarbonate resin (A), or composed of a polycarbonate resin (A) and a graft copolymer (B);

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

the graft copolymer (B) is a polymer 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),

in the resin main component (C), the content of the polycarbonate resin (A) is 80-100 mass%, the content of the graft copolymer (B) is 0-20 mass%, and the total content of the polycarbonate resin (A) and the graft copolymer (B) is 100 mass%,

the polyester resin (F) contains a dicarboxylic acid component containing a cyclic phosphorus compound represented by the following formula (1), and the content of phosphorus atoms in the polyester resin (F) is 4 to 6 mass%,

the proportion of the inorganic filler (D) is 20 to 50% by mass relative to 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 content of the modified polyester resin (H) containing phosphorus is 3 to 10 parts by mass per 100 parts by mass of the resin main component (C),

[ chemical formula 1]

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

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

4. The reinforced thermoplastic resin composition of any of claims 1 to 3, wherein the reinforced thermoplastic resin composition further comprises a phosphate-based flame retardant (I).

5. A molded article obtained by molding the reinforced thermoplastic resin composition according to any one of claims 1 to 4.