JP2021014528A - Resin composition, molded body, electronic part, and electronic device - Google Patents

Abstract

To provide a resin composition excellent in all of cost, mechanical strength, and flame retardancy.SOLUTION: A resin composition comprises a PC resin, a PS resin, an ABS resin, a modified PP resin with a graft-bonded maleic anhydride, and phosphorus compounds. The amount of the PC resin is from 40 to 90 pts.mass with respect to 100 pts.mass of all the resins. The amount of the modified PP resin with a graft-bonded maleic anhydride is 3 pts.mass or more with respect to 100 pts.mass of all the resins.SELECTED DRAWING: None

Description

The present invention relates to resin compositions, molded articles, electronic components, and electronic devices.

Since polymers, which are generally organic substances, burn in the event of a fire, flame retardant resins with flame retardants added are widely used in automobile materials, electrical and electronic equipment materials, housing materials, and materials for manufacturing parts in other processing fields. There is. It is necessary for such a resin material not only to withstand combustion but also to maintain its shape without being deformed before self-extinguishing even if it catches fire. Furthermore, it is required that not only such flame retardancy but also mechanical properties are good, and in particular, it is necessary to withstand impact strength. In order to realize this, a resin composition obtained by blending ABS resin or polystyrene (PS) resin with polycarbonate (PC) resin, which is widely used in the market because a good appearance can be easily obtained by injection molding. It has been known. In particular, it is known to use a PC / PS alloy for the purpose of cost reduction.

Patent Document 1 discloses a resin composition containing a PC resin, other resins, and a phosphorus-containing compound for the purpose of providing a resin composition having particularly excellent flame retardancy, rigidity, and impact resistance. There is. It is a resin composition having excellent flame retardancy, rigidity, and impact resistance, and the composition of 80 parts by mass of PC resin, 16 parts by mass of ABS resin, and 4 parts by mass of PS resin is disclosed with respect to 100 parts by mass of resin. ing.

An object of the present invention is to provide a resin composition having excellent low cost, mechanical strength, and flame retardancy.

The resin composition of the present invention that solves the above problems is as follows.
(1) A resin composition containing a PC resin, a PS resin, an ABS resin, a modified PP resin graft-bonded with maleic anhydride, and a phosphorus-based compound.
The PC resin is contained in an amount of 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total resin.
A resin composition containing 3 parts by mass or more of the modified PP resin graft-bonded with maleic anhydride with respect to 100 parts by mass of the total resin.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition which suppresses cost and is excellent in mechanical strength and flame retardancy.

Embodiments of the present invention will be described. The resin composition of the present invention is shown in (1) below, but the embodiments (2) to (11) are also included in the embodiments thereof, and these will also be described.
(1) A resin composition containing a PC resin, a PS resin, an ABS resin, a modified PP resin graft-bonded with maleic anhydride, and a phosphorus-based compound.
The PC resin is contained in an amount of 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total resin.
A resin composition containing 3 parts by mass or more of the modified PP resin graft-bonded with maleic anhydride with respect to 100 parts by mass of the total resin.
(2) The resin composition according to (1) above, wherein the acid value of the modified PP resin graft-bonded with maleic anhydride is 3.5 mgKOH / g or more and 52 mgKOH / g or less.
(3) The resin composition according to (1) or (2) above, which contains 3 parts by mass or more and 40 parts by mass or less of the modified PP resin graft-bonded with the maleic anhydride with respect to 100 parts by mass of the total resin.
(4) At least one of the phosphorus compounds is a phosphazene compound, and the phosphazene compound is contained in an amount of 0.1 part by mass or more and 4.0 parts by mass or less based on 100 parts by mass of the total resin (1). The resin composition according to any one of 3).
(5) The phosphorus compound contains a phosphazene compound and a phosphorus compound other than the phosphazene compound, and the phosphorus compound other than the phosphazene compound is red phosphorus and / or a phosphoric acid ester (1). ) To (4).
(6) The resin composition according to any one of (1) to (5) above, wherein the total content of the phosphorus compound is less than 16 parts by mass with respect to 100 parts by mass of the total resin.
(7) The resin composition according to any one of (1) to (6) above, wherein the Charpy impact strength at 23 ° C. is 7.0 kJ / m ² or more.
(8) The resin composition according to any one of (1) to (7) above, which has a tensile strength of 40 MPa or more.
(9) A molded product made of the resin composition according to any one of (1) to (8) above.
(10) An electronic component having the molded product according to (9) above.
(11) An electronic device having the molded product according to (9) above.

The resin composition of the present invention contains a PC resin, a PS resin, an ABS resin, a modified PP resin graft-bonded with maleic anhydride, and a phosphorus-based compound, and the PC resin is 40 parts by mass based on 100 parts by mass of the total resin. 3 parts or more and 90 parts by mass or less, and 3 parts by mass or more of the modified PP resin graft-bonded with the maleic anhydride is contained with respect to 100 parts by mass of the total resin.
The number of parts by mass with respect to 100 parts by mass of the total resin is the number of parts by mass when the total of all the resins contained in the resin composition is 100 parts by mass.
PC resin is excellent in mechanical strength and flame retardancy, but the cost is high. It is conceivable to increase the amount of PS resin by using a PC / PS alloy in order to reduce the cost, but the compatibility is deteriorated, and the mechanical strength and flame retardancy are lowered. In the resin composition of the present invention, the PC resin is 40 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the total resin, and the ABS resin, PS resin, and maleic anhydride of 3 parts by mass or more based on 100 parts by mass of the total resin. Contains graft-bonded PP resin. In the resin composition of the present invention, PS resin and ABS resin are dispersed in a matrix of PC resin to form a sea-island structure. By adopting such a composition, ABS resin is compatible with PS resin. It is easy to use, and by improving the compatibility between the PC resin and the PS resin, the dispersed state of the PS resin is stabilized, and the modified PP resin graft-bonded with maleic anhydride reduces the interfacial tension between the resins, resulting in island grains. By reducing the diameter, improving the interfacial adhesion, and improving the dispersibility of the phosphorus-based compound, it is possible to prevent a decrease in mechanical strength and flame retardancy while suppressing the cost.

Hereinafter, each component of the resin composition of the present invention, such as a PC resin, a PS resin, an ABS resin, a modified PP resin graft-bonded with maleic anhydride, a phosphorus-based compound, and other additives, will be described in detail. To do.

(PC resin)
The polycarbonate resin may be, for example, an aromatic homopolycarbonate resin or a copolycarbonate resin obtained by reacting an aromatic dihydric phenolic compound with phosgene or a carbonic acid diester. Examples of aromatic dihydric phenolic compounds include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4-hydroxyphenyl). ) Methan, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2 -Bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1 Examples thereof include −phenyl-1,1-bis (4-hydroxyphenyl) ethane, and these may be used alone or as a mixture.

As the polycarbonate resin, a synthetic one may be used, or a commercially available product may be used. Commercially available products include, for example, "L-1250Y" and "AD5503" manufactured by Teijin Chemicals Ltd., "A2200" manufactured by Idemitsu Kosan Co., Ltd., "Iupilon S2000" and "Iupilon H-3000VR" manufactured by Mitsubishi Engineering Plastics Co., Ltd. Group polycarbonate resin) and the like.
Further, the polycarbonate resin may be used alone or in combination of two or more.

Further, the polycarbonate resin may be a market-recovered material collected from the market, and may include, for example, a waste disk such as a waste CD or a recycled material such as a waste bottle such as a gallon bottle of a water server.

The resin composition of the present invention contains 40 parts by mass or more and 90 parts by mass or less of the PC resin with respect to 100 parts by mass of the total resin. It is preferably contained in an amount of 45 parts by mass or more and 80 parts by mass or less, and more preferably 45 parts by mass or more and 70 parts by mass or less. In a resin composition containing a modified PP resin graft-bonded with PC resin, PS resin, ABC resin, and maleic anhydride, the content of PC resin is 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total resin. If there is, it is possible to reduce the cost while maintaining the mechanical strength and flame retardancy.

(PS resin)
The polystyrene resin has a structural unit represented by the following general formula, and preferably contains a rubber component.

Specific examples of the polystyrene resin include a rubber-modified styrene polymer obtained by dissolving a rubber component in a styrene-based monomer and a known polymerization method such as a massive polymerization method or a suspension polymerization method, or a styrene-based monomer. Examples thereof include those in which a rubber component is physically mixed by a known method to form a mixture of a styrene-based monomer and a rubber component.
As the above-mentioned styrene-based monomer, styrene is preferably used. If necessary, for example, α-methylstyrene, α-methyl-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, pt- Butylstyrene, 1,1-diphenylethylene, bromostyrene, dibromostyrene, chlorostyrene, dichlorostyrene and the like can also be used in combination with styrene as a styrene-based monomer. When two or more types of styrene-based monomers are used, it is preferable to contain 50 parts by mass or more of styrene.
Examples of the rubber component include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyisoprene, styrene-isoprene copolymer, butadiene-methacrylic acid ester copolymer, acrylic rubber, and ethylene-. Examples thereof include propylene rubber, ethylene-propylene-diene rubber, and hydrogenated diene rubber. These rubber components may be used alone or in combination of two or more, and when two or more types of rubber components are used, the mixing ratio thereof is not particularly limited.

Further, the polystyrene resin may be a market-recovered material collected from the market, and may include, for example, a recycled material such as home appliances such as air conditioners, televisions, refrigerators and washing machines, and used OA equipment.
The cost of the resin composition of the present invention can be reduced by containing the PS resin. The higher the content of the PS resin in the resin composition, the lower the cost. However, considering the range in which the cost can be reduced and good mechanical strength and flame retardancy can be obtained, the PS resin in the resin composition can be reduced in cost. The content is preferably 2 parts by mass or more and less than 30 parts by mass with respect to 100 parts by mass of the total resin.

(ABS resin)
The method for producing the ABS resin is not particularly limited, but is an emulsified polymerization method in which an emulsified rubber is mixed with an emulsified styrene or acrylic nitrile monomer and polymerized; the rubber is dissolved in a styrene or acrylic nitrile monomer and polymerized. It can be produced by a massive suspension polymerization method or the like in which massive polymerization is carried out, and the polymerization solution is suspended in water during the polymerization to continue the polymerization under suspension polymerization conditions. When alloying a PC resin, PS resin, or the like, a polymerization method is selected according to the characteristics of the ABS resin used, but in general, either an emulsion polymerization method or a massive suspension polymerization method is used. The ABS resin produced by the method can also be alloyed.

Further, the ABS resin may be a market-recovered material collected from the market, and may contain, for example, a recycled material such as home appliances such as air conditioners, televisions, refrigerators, and washing machines, and used OA equipment.

The content of the ABS resin is preferably equal to or less than the content of the PS resin. That is, it is preferable that the number of parts by mass of the ABS resin with respect to 100 parts by mass of the total resin is the same as or less than the number of parts by mass of the PS resin with respect to 100 parts by mass of the total resin. By adding a small amount of ABS resin, the compatibility between the PC resin and the PS resin can be improved, and the dispersibility of the PS resin can be improved. That is, ABS resin is used like a compatibilizer.
From the viewpoint of low cost, mechanical strength, and flame retardancy, the ABS resin is preferably contained in an amount of 1 part by mass or more and 20 parts by mass or less. However, when the content of the ABS resin is larger than the content of the PS resin, the PS resin is contained. Dispersibility deteriorates, and it is difficult to obtain sufficient flame retardancy and impact resistance. By containing the ABS resin in an amount equal to or less than the content of the PS resin, the compatibility between the PC resin and the PS resin can be improved, and the dispersibility of the PS resin can be improved.

(Modified PP resin graft-bonded with maleic anhydride)
As the modified PP resin graft-bonded with maleic anhydride, a synthesized one may be used, or a commercially available product may be used. Examples of commercially available products include "Youmex 1010", "Youmex 100TS", "Youmex 1001", "Youmex 5500" manufactured by Sanyo Chemical Industries, Ltd., and "Kayabrid" manufactured by Explosives Akzo.
Further, the modified PP resin graft-bonded with maleic anhydride may be used alone or in combination of two or more.

The resin composition of the present invention needs to contain 3 parts by mass or more of the modified PP resin graft-bonded with maleic anhydride with respect to 100 parts by mass of the total resin, and contains 3 parts by mass or more and 40 parts by mass or less. Is preferable.
By containing 3 parts by mass or more of the modified PP resin graft-bonded with maleic anhydride with respect to 100 parts by mass of the total resin, the island particle size is reduced, the interfacial adhesion is improved, and the dispersibility of the phosphorus compound is also improved. .. Further, when it is 40 parts by mass or less, the mechanical strength does not decrease.

The modified PP resin graft-bonded with maleic anhydride preferably has an acid value of 3.5 mgKOH / g or more and 52 mgKOH / g or less. When the acid value is 52 mgKOH / g or less, molecular cleavage is prevented and the molecular weight is less likely to decrease, and when the acid value is 3.5 mgKOH / g or more, a compatibility effect can be obtained. The acid value of the modified PP resin graft-bonded with maleic anhydride is more preferably 10 mgKOH / g or more and 52 mgKOH / g or less.

(Other resins)
The resin composition of the present invention is a modified PP resin obtained by graft-bonding a PC resin, a PS resin, an ABS resin, and maleic anhydride, and a PE resin as long as the flame retardancy, rigidity, impact resistance, etc. are not significantly reduced. Can be contained.

(Phosphorus compound)
The resin composition of the present invention contains a phosphorus compound as a flame retardant. At least one of the phosphorus compounds is preferably a phosphazene compound, and it is preferable that the phosphorus compound is contained in an amount of 0.1 part by mass or more and 4.0 parts by mass or less based on 100 parts by mass of the total resin.
It is preferable that the phosphorus-based compound contains a phosphazene-based compound and a phosphorus-based compound other than the phosphazene-based compound, and the phosphorus-based compound other than the phosphazene-based compound is red phosphorus and / or a phosphoric acid ester.
Further, the total content of the phosphorus compound is preferably less than 16 parts by mass with respect to 100 parts by mass of the total resin in order to prevent a decrease in mechanical strength.

前記一般式中、Ｘは、それぞれ独立して、ハロゲン原子、もしくは芳香族鎖、脂肪族鎖を表す。
さらに、前記ホスファゼン系化合物はその製造法により、環状の構成数が増加することがあるが、特に制限はなく、目的に応じて適宜選択することができる。
前記一般式における側鎖基Ｘの脂肪族鎖、芳香族鎖はアルコキシ基構造を有しても良いし、末端にハロゲン元素を有しても良い。
アルコキシ基を形成する化合物は、脂肪族系化合物、芳香族系化合物など何でも良いが、芳香族環を含む化合物がホスファゼン系化合物の安定性のためとリン系化合物への溶解性のために好ましい。
これらの中でも、Ｘは、フェノキシ基が好ましい。 (Phosphazene compound)
As for the phosphazene compound, a phosphazene compound represented by the following general formula is preferable in terms of ease of production and stability of the compound.

In the above general formula, X independently represents a halogen atom, an aromatic chain, or an aliphatic chain.
Further, the number of cyclic constituents of the phosphazene compound may increase depending on the production method thereof, but there is no particular limitation, and the phosphazene compound can be appropriately selected depending on the intended purpose.
The aliphatic chain and aromatic chain of the side chain group X in the above general formula may have an alkoxy group structure or may have a halogen element at the terminal.
The compound forming the alkoxy group may be any compound such as an aliphatic compound and an aromatic compound, but a compound containing an aromatic ring is preferable because of the stability of the phosphazene compound and the solubility in a phosphorus compound.
Among these, X is preferably a phenoxy group.

The phosphazene compound is preferably contained in an amount of 0.1 part by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the total resin of the resin composition, and 1.0 part by mass with respect to 100 parts by mass of the total resin. More preferably, it is contained in an amount of 3.0 parts by mass or less.
When the content is 0.1 parts by mass or more, the flame retardancy is excellent. If it is contained in an amount exceeding 4.0 parts by mass, it tends to aggregate in the flame-retardant resin during kneading, which is not preferable. When the content is 4.0 parts by mass or less, it is difficult to aggregate in the flame-retardant resin, and the flame-retardant property is excellent.

(Phosphorus compounds other than phosphazene compounds)
In the present invention, it is preferable to use a phosphorus compound other than the phosphazene compound in combination with the phosphorus compound in order to prevent the aggregation of the phosphazene compound described above.
As the phosphorus-based compound other than the phosphazene-based compound, red phosphorus, phosphoric acid ester, ammonium polyphosphate, sodium polyphosphate, metal phosphinic acid salt and the like are used, and red phosphorus and phosphoric acid ester are preferably used. The phosphorus compound in the present invention also includes a simple substance of phosphorus.
Above all, it is preferable to use a phosphoric acid ester that melts at a kneading temperature.
That is, the phosphoric acid ester is a compound having a melting point (Tm), and Tm is preferably less than 300 ° C., more preferably less than 200 ° C., and particularly preferably less than 100 ° C. The most preferable lower limit of Tm is 0 ° C. or higher, but the lower limit of Tm is not limited by the present invention as long as it is in a molten state during kneading. However, if Tm is less than −40 ° C., it is not preferable because when it is dispersed in the resin, it floats to the surface over time and bleed-out becomes severe.
Among the phosphoric acid esters, there are compounds that are three-dimensionalized, do not melt during kneading, and do not have Tm, and such compounds are not suitable in the present invention.

前記一般式（２）中、Ｒ³〜Ｒ⁷は、それぞれ独立して、芳香族環を含む基を表す。ｎは、１〜１０，０００を表す。 Next, the phosphoric acid ester will be exemplified, but this example does not particularly limit the present invention.
For example, one or a mixture of tri (alkylphenyl) phosphate, di (alkylphenyl) monophenyl phosphate, diphenyl mono (alkylphenyl) phosphate or triphenyl phosphate, or a mixture represented by the following general formula (2). One or a mixture of two or more compounds.

In the general formula (2), R ^{3 to} R ⁷ each independently represent a group containing an aromatic ring. n represents 1 to 10,000.

From R ³ to R ⁷ , aryl or alkyl-substituted aryl groups are preferred, preferably R ³ , R ⁴ , R ⁶ and R ⁷ are phenyl groups or methyl, ethyl, isopropyl, t-butyl, isobutyl, isoamyl, A phenyl group substituted with an alkyl group such as t-amyl, more preferably a phenyl group or a phenyl group substituted with a methyl, ethyl, isopropyl or t-butyl group; R ⁵ is an aryl or alkyl. Substituted aryl group derivatives are preferred, and those derived from resorcinol, hydroquinone or bisphenol-A are more preferred.

The phosphorus compound may be added at the time of kneading the resin composition of the present invention, or may be kneaded in advance with a polymer other than the PC resin, and this composition may be added at the time of kneading the resin composition. ..

The total content of the phosphorus compound including the phosphazene compound is preferably less than 16 parts by mass with respect to 100 parts by mass of the total resin, and is 3.5 parts by mass or more and 16 parts by mass in order to prevent a decrease in mechanical strength. Less than a portion is more preferable. If it is less than 16 parts by mass, the impact strength does not decrease.
In the case of a phosphoric acid ester, the content of the phosphorus compound other than the phosphazene compound is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, based on 100 parts by mass of the total resin. In the case of red phosphorus, since the phosphorus content is high, a flame retardant effect can be obtained with a small amount. It is preferably 1 part by mass or more and less than 8 parts by mass with respect to 100 parts by mass of the total resin. If it is less than 8 parts by mass, it does not affect the physical properties.

(Other additives)
The resin composition of an example of the present invention may contain other additives such as stabilizers and dyes and pigments as long as the flame retardancy, rigidity, impact resistance and the like are not significantly reduced.

As a method for identifying the contained resin or the like from the resin composition, infrared spectroscopy is used, the resin structure and the phosphorus-based compound are observed from the composition image, and the respective spectra are obtained to obtain the resin and the phosphorus-based compound. And the like.
If the compositions match, a calibration curve for each resin can be prepared using GCMS to quantify each resin.
Phosphorus compounds can be solvent-extracted and quantified by GCMS in the same manner as resins.

The resin composition of the present invention preferably has a Charpy impact strength of 7.0 kJ / m ² or more at 23 ° C. of the molded test piece. When the Charpy impact strength is 7.0 kJ / m ² or more, it can be said that the toughness is high. The Charpy impact strength is more preferably 10.0 kJ / m ² or more, and even more preferably 15.0 kJ / m ² or more.
The Charpy impact strength was measured at 23 ° C. by preparing a notched impact test piece and using a Charpy impact tester in accordance with ISO179-1.
Further, in the resin composition of the present invention, the tensile strength of the molded test piece at 23 ° C. is preferably 40 MPa or more. When the tensile strength is 40 MPa or more, it can be said that the rigidity is high. The tensile strength is more preferably 50 MPa or more, still more preferably 60 MPa or more.
Tensile strength was measured at 23 ° C. in accordance with ISO527-2.

Explanation of electronic devices (about molded products)
The molded article of an example of the present invention (hereinafter, also referred to as “an example molded article”) comprises the resin composition of an example of the present invention.
Examples of the molded body include information / mobile devices such as computers, notebook personal computers, tablet terminals, smartphones, and mobile phones, and members of OA devices such as printers and copiers. In particular, it is preferably used for exterior members that require heat resistance.
An example molded body can be obtained, for example, by injection molding an example resin composition according to a conventional method.

(Electronic parts, electronic devices)
The electronic component of an example of the present invention has the molded product of the present invention.
The electronic device of an example of the present invention has the molded product of the present invention.

Examples of the electronic components include information / mobile devices such as computers, notebook computers, tablet terminals, smartphones and mobile phones, and electronic components such as OA devices such as printers and copiers.
Examples of the electronic devices include information / mobile devices such as computers, notebook personal computers, tablet terminals, smartphones, and mobile phones, OA devices such as printers and copiers, and home appliances such as televisions, refrigerators, and vacuum cleaners. Can be mentioned.

(Manufacturing method of resin composition)
An example of the method for producing the resin composition of the present invention (hereinafter, also referred to as “an example production method”) includes, for example, a PC resin, a PS resin, an ABS resin, a modified PP resin obtained by graft-bonding maleic anhydride, and a phosphorus-based resin. It comprises a melt-kneading step of melt-kneading a compound and optionally added components, as well as other additives added as needed.

<Melting and kneading process>
In the production method of one example, first, the components necessary for the present invention, the components optionally added, and other additives added as needed are melt-kneaded (melt-kneading step).
According to the above step, each component can be uniformly mixed.
In this step, each of the above components is kneaded using a kneader known in the art such as a tumbler, a Henschel mixer, a Banbury mixer, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader. Knead while appropriately adjusting conditions such as speed, kneading temperature, and kneading time.

For example, each of the above components is mixed in advance using a tumbler, a Henschel mixer or the like, and then melt-kneaded by a kneader such as a Banbury mixer, a roll, a lavender, a single-screw kneading extruder, a twin-screw kneading extruder or a kneader. You may. Further, for example, these components may be put into an extruder using a feeder and melt-kneaded without mixing the components in advance. Further, for example, the resin composition obtained by premixing only a part of the components and then melt-kneading may be used as a masterbatch, and the masterbatch and the remaining components may be melt-kneaded again.

Here, in this step, without particular limitation, it is also preferable that the arbitrarily selected components are melt-mixed in advance and then added to the twin-screw kneading extruder. When the phosphate ester is liquid at room temperature, it is possible to dissolve the phosphazene compound in this component at room temperature. When the phosphate ester is solid (for example, powder) at room temperature, these components are mixed in a mortar, and then the mixture is heated to 90 ° C. or higher to melt the mixture, and the mixed mixture in the molten state is mixed with a twin-screw kneading extruder. Can be added to.

The premixing of the phosphoric acid ester and the phosphazene compound is an example of the melt-kneading step, and is a preferable embodiment from the viewpoint of enhancing the dispersibility of the phosphorus compound. It is not essential in the production method of the present invention. Further, the mixing using the mortar is an example of the mixing method, and the mixing method in the production method of the present invention is not limited to this, and may be any method.

In particular, the kneading temperature is determined based on the melting temperature (Tm) of the PC resin. For the measurement of Tm, any measured value such as DSC, TMA, DTA, and a viscoelastic device whose temperature can be changed may be used as in the case of the glass transition point (Tg), but the measurement was performed using these devices. The resin composition of the present invention can be easily obtained by kneading at a temperature near Tm.

Further, below this Tm temperature, the shear flow works effectively and inhibits the domain formation of the phosphazene compound, which is preferable. In particular, it is possible to obtain the preferable results of the present invention in the temperature range of the kneading temperature of less than Tm to Tg + 20 ° C.

It is known that Tm and Tg vary depending on the measurement method. In the present invention, it is preferable to use the values of Tm and Tg measured by DSC.

(Examples 1 to 14, Comparative Examples 1 to 2)
The raw materials are mixed according to the composition (part by mass) shown in Table 1, and the raw materials are mixed at a cylinder temperature of 230 ° C. using a twin-screw melt-kneading extruder (manufactured by Technobel) having a screw diameter of 25 mm and an effective screw length of L / D = 26. It was smelted to obtain a resin composition.
Next, using the obtained resin composition, it was melted at a set temperature of 240 ° C. and injection molded to obtain an evaluation piece.

The raw materials listed in Table 1 are as follows.
In Table 1, the column of "number of copies" indicates the amount (parts by mass) of the blended raw material, and the column of "ratio" indicates the number of copies by mass with respect to 100 parts by mass of the total resin.
Raw material Resin PC resin: H-3000VR (manufactured by Mitsubishi Engineering Plastics)
PS resin: H650 (manufactured by Toyo Styrene Co., Ltd.)
ABS resin: 250-X10 (manufactured by Toray Industries, Inc.)
Modified PP resin (MA-PP resin) graft-bonded with maleic anhydride:
Youmex 1010 (Sanyo Chemical Industries, Ltd.), acid value 52 mgKOH / g
Youmex 100TS (Sanyo Chemical Industries, Ltd.), acid value 3.5 mg KOH / g
Youmex 1001 (Sanyo Chemical Industries, Ltd.), acid value 26 mgKOH / g
Phosphorus compounds Phosphazene compounds: SPS100
(Manufactured by Otsuka Chemical Co., Ltd., has a 6-membered ring cyclic structure as the main component, 6 of which
Aromatic phosphazene compounds whose side chains are all phenoxy groups)
Phosphate ester: PX-200
(Manufactured by Daihachi Chemical Co., Ltd., aromatic condensed phosphoric acid ester, melting point 92 ° C or higher),
Red phosphorus: High-purity red phosphorus (manufactured by Nippon Chemical Industrial Co., Ltd.)

Evaluation test method The following evaluation was performed using the obtained evaluation pieces. The results are shown in Table 1.
(Impact test)
An impact test was performed at 23 ° C. using a Charpy impact tester in accordance with ISO179-1.
The test piece was provided with a notch. The higher the measured value (kJ / m ² ), the better the impact resistance was evaluated.
Evaluation Criteria ◎: 15.0 kJ / m ² or more 〇: 10.0 kJ / m ² or more and less than 15.0 kJ / m ² Δ: 7.0 kJ / m ² or more and less than 10.0 kJ / m ² ×: 7.0 kJ / m Less than ²

(Tensile test)
Tensile tests were performed at 23 ° C. in accordance with ISO527-2. It was evaluated that the higher the measured value (MPa), the better the rigidity (tensile strength).
Evaluation Criteria ⊚: 60 MPa or more 〇: 50 MPa or more and less than 60 MPa Δ: 40 MPa or more and less than 50 MPa ×: less than 40 MPa

(Combustion test)
A flame retardant test was conducted in accordance with the UL94 test (combustion test of plastic materials for equipment parts) established by the US Underwriters Laboratories (UL). The thickness t of the test piece was 1.5 mm.
First, a UL94V test was performed to determine "V-0", "V-1", and "V-2".
Next, in the UL94V test, a UL94-5V test was performed on a material conforming to the "V-0" or "V-1" rank, and "5V-A" and "5V-B" were determined. ..
In the UL94-5V test, the cases of "5V-A" and "5V-B" are acceptable.

(PS resin ratio)
The cost was evaluated by the numerical value of the ratio of PS resin.
[Evaluation criteria]
Rank compounding ratio (number of compounding masses to 100 parts by mass of resin)
◎: 25 or more 〇: 15 or more and less than 25 Δ: 2 or more and less than 15 ×: less than 2

JP-A-2017-0956667

Claims (11)

A resin composition containing a PC resin, a PS resin, an ABS resin, a modified PP resin graft-bonded with maleic anhydride, and a phosphorus-based compound.
The PC resin is contained in an amount of 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the total resin.
A resin composition containing 3 parts by mass or more of the modified PP resin graft-bonded with maleic anhydride with respect to 100 parts by mass of the total resin. The resin composition according to claim 1, wherein the modified PP resin graft-bonded with maleic anhydride has an acid value of 3.5 mgKOH / g or more and 52 mgKOH / g or less. The resin composition according to claim 1 or 2, which contains 3 parts by mass or more and 40 parts by mass or less of the modified PP resin graft-bonded with maleic anhydride with respect to 100 parts by mass of the total resin. The phosphorus-based compound is at least one type of phosphazene-based compound, and according to any one of claims 1 to 3, the phosphazene-based compound is contained in an amount of 0.1 part by mass or more and 4.0 parts by mass or less based on 100 parts by mass of the total resin. The resin composition described. Claims 1 to 4 wherein the phosphorus compound contains a phosphazene compound and a phosphorus compound other than the phosphazene compound, and the phosphorus compound other than the phosphazene compound is red phosphorus and / or a phosphoric acid ester. The resin composition according to any one. The resin composition according to any one of claims 1 to 5, wherein the total content of the phosphorus-based compound is less than 16 parts by mass with respect to 100 parts by mass of the total resin. The resin composition according to any one of claims 1 to 6, wherein the Charpy impact strength at 23 ° C. is 7.0 kJ / m ² or more. The resin composition according to any one of claims 1 to 7, wherein the tensile strength is 40 MPa or more. A molded product made of the resin composition according to any one of claims 1 to 8. An electronic component having the molded product according to claim 9. An electronic device having the molded product according to claim 9.