TW201326281A - Resin composite - Google Patents

Abstract

A resin composite is disclosed, which comprises: a thermo plastic resin; a sheet-type graphite; and a carbon fiber. The resin composite of the present invention enables the product provided there from to have excellent IZOD impact strength and high thermo conductivity coefficient so as to lengthen the lifespan and increase the commercial benefit.

Description

Resin composition

The present invention relates to a resin composition, and more particularly to a resin composition which can improve impact strength and maintain excellent heat transfer coefficient.

Polycarbonate resins are widely used in various fields of daily life because of their excellent mold and shape. However, since the polycarbonate resin itself has low fluidity and impact. In order to improve this deficiency, the industry has tended to develop such a demand by means of resin blending and the like. Among them, aromatic vinyl compounds are most widely used.

ABS (styrene-butadiene-propylene graft copolymer) resin formed by graft copolymerization of an aromatic vinyl compound and a vinyl cyanide compound on a rubbery polymer is a representative resin composition because of its superiority The formability, physical properties, mechanical strength, impact resistance and surface gloss are widely used in various fields such as electronics, electrical appliances (such as household appliances) or automotive supplies.

However, when used in the automotive field, home appliances, business machine applications, etc., especially when used as an external component, there is often a problem of insufficient punching resistance, so that the service life cannot be extended.

In order to improve the impact resistance, the particle diameter distribution of the rubber-like dispersed particles is often limited, and this is also a conventionally known method. In addition, a polycarbonate resin, an acrylonitrile-diene-styrene resin (abbreviated as ABS resin), a (meth)acrylate-diene-styrene resin (abbreviated as MBS resin), Or blended with impact-resistant polystyrene resin (abbreviated as HIPS resin). However, when the ABS resin or the MBS resin is blended, the impact resistance of the polycarbonate resin can be improved, but the improvement in the fluidity of the molding process is not sufficient. On the other hand, when the HIPS resin is used, since the compatibility between the polycarbonate resin and the HIPS resin is not good, the dispersibility of the blend is poor.

In addition, with the rapid development of the semiconductor industry in recent years, and with the development trend of high-density packaging of electronic products, heat dissipation problems such as semiconductor devices and electronic products have become a research and development focus. For example, mobile phones or tablet computers have been developed in terms of small size, light weight, and styling. Therefore, there is an increasing demand for resin materials having high impact resistance and moldability and high heat dissipation.

However, currently known improvements in technology and products are still not meeting the current needs. Therefore, there is still a need in the art to develop new and improved formulations that can continuously improve the impact strength and maintain a high heat transfer coefficient, and can have a long service life.

Accordingly, the present invention provides a resin composition comprising: a thermoplastic resin; a scaly type graphite; and a carbon fiber.

The sample prepared by extruding and ejecting the resin composition of the present invention can have excellent Izod impact strength (test results are all higher than 70 J/m), and also maintain a high heat transfer coefficient (experimental result measurement) It can be 1.32 W/m*K or more). Therefore, the improved formulation of the resin composition of the present invention can increase the service life of the sample and maintain a high heat transfer coefficient, thereby improving its commercial value.

In the resin composition of the present invention, the content of the thermoplastic resin may preferably be 65 to 75 parts by weight based on 100 parts by weight of the total weight of the resin composition; and the content of the scale-type graphite may preferably be 20 to 30 Parts by weight. When the content of the flake type graphite is less than 20 parts by weight, the thermal conductivity tends to decrease, and when the content is more than 30 parts by weight, the surface appearance and workability are not good. The content of the carbon fibers may be from 3 to 13 parts by weight, more preferably from 5 to 12 parts by weight. When the content of the carbon fibers is less than 3 parts by weight, the thermal conductivity tends to decrease, and when the content is more than 13 parts by weight, the productivity and workability are poor.

In the resin composition of the present invention, the carbon fiber is not particularly limited. The length of the carbon fibers may preferably be from about 3 to 9 mm, most preferably from 5 to 7 mm (i.e., 6 ± 1 mm). In addition, carbon fibers may be partially or completely substituted with glass fibers.

In the resin composition of the present invention, the scaly type graphite preferably comprises at least two kinds of flaky graphite of a particle size. For example, in the resin composition of the present invention, the flaky graphite type includes: flaky graphite having an average particle diameter of 30 μm to 40 μm; and flaky graphite having an average particle diameter of 300 μm to 400 μm. Further, in the resin composition of the present invention, the weight ratio of the flaky graphite having an average particle diameter of 30 μm to 40 μm to the flaky graphite having an average particle diameter of 300 μm to 400 μm may be, for example, 1:5~. 1:7.

The present invention can achieve the effect of improving the impact strength by simultaneously using two kinds of flaky graphite of different particle diameters and adding carbon fiber in the resin composition, and at the same time maintaining excellent heat conduction characteristics, which is not known in the prior art. Unique features.

In the resin composition of the present invention, any thermoplastic resin suitable for extrusion or injection molding can be used as the thermoplastic resin of the present invention, such as a thermoplastic plastic and a thermoplastic engineering grade plastic which are generally used. For example, the thermoplastic resin may include a polyethylene resin, a polypropylene resin, a polyvinyl chloride resin, a polystyrene resin, a styrene graft copolymer resin, or a styrene-butadiene copolymer resin. Polyamide resin, polyoxymethylene resin, polycarbonate resin, polymethyl methacrylate resin, liquid crystal polymer resin, polyvinylidene fluoride resin, polyphenylene ether resin, or polyphenylene sulfide Resin. The above resin may be a copolymer or a mixture of two or more.

Preferably, in the present invention, the thermoplastic resin comprises at least one selected from the group consisting of polystyrene resins and non-polystyrene resins; more preferably at least one selected from the group consisting of polystyrene graft copolymer resins. And polycarbonate resin. For example, in the resin composition of the present invention, the polystyrene-based graft copolymer resin may be a methyl methacrylate-conjugated diene rubber-styrene graft copolymer or a styrene-conjugated two. An olefin rubber-acrylonitrile-based graft copolymer.

The styrene monomer of the present invention may be: styrene, α-methylstyrene, m-chlorostyrene, p-tert-butylstyrene, p-methylstyrene, o-chlorostyrene, or the like. -chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromostyrene, or 2,5-dibromostyrene, among others, styrene Or α-methylstyrene is preferred.

The conjugated diene rubber suitable for use in the present invention is preferably a butadiene rubber, an isoprene rubber, or a chloroprene rubber; among them, the butadiene rubber has a high cis (Hi-Cis) content. And low cis (Los-Cis) content; in high cis rubber, the typical weight composition of cis (Cis) / vinyl (Vinyl) is 94 ~ 98% / 1 ~ 5%, the rest of the composition is reverse Trans (Trans) structure; its Mooney viscosity is between 20 and 120, and the molecular weight range is from 100,000 to 800,000; in low cis rubber, the typical weight composition of cis/vinyl is 20-40%/1 to 20%. The rest is a trans structure; its Mooney viscosity is between 20 and 120; other suitable rubber materials are: propylene rubber, styrene/butadiene rubber, or a mixture of the above different rubbers, styrene/butadiene rubber Commonly known as SBR; a styrene/butadiene copolymerized rubber suitable for the present invention, the polymerization type of which can be a di-block copolymerization, a tri-block copolymerization, a random copolymer (random) or star type. The weight ratio of the styrene/butadiene rubber is preferably from 5/100 to 80/20, and the molecular weight range is preferably from 50,000 to 600,000; the above-mentioned rubber suitable for the present invention is butadiene rubber and styrene/butadiene. The olefin rubber is preferred, and the butadiene rubber is more preferred.

The acrylonitrile-based monomer used in the present invention may be: acrylonitrile or α-methacrylonitrile, and among them, acrylonitrile is preferable; and the (meth) acrylate monomer may be: methacrylic acid Ester, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, methacrylic acid 2-hydroxyethyl ester, glycidyl methacrylate, dimethylaminoethyl methacrylate, or methyl acrylate and butyl acrylate, etc., of which methyl methacrylate or butyl acrylate is preferred.

The polycarbonate-based resin used in the present invention may be any single-comon polycarbonate or copolycarbonate known in the art, and the above-mentioned polycarbonate-based resin may be prepared according to any process known in the art. For example, utilizing interfacial polycondensation processes, polycondensation in homogeneous phase, or transesterification, such processes and combinations of reactants, polymers, catalysts, solvents, and conditions are well known in the art, suitable Polycarbonates can be selected from the following bisphenols: dihydroxybiphenyl, bis-(hydroxyphenyl)-alkane, bis-(hydroxyphenyl)-bis, bis-(hydroxyphenyl)-sulfide, double -(hydroxyphenyl)-ether, bis-(hydroxyphenyl)-one, bis-(hydroxyphenyl)-arylene, bis-(hydroxyphenyl)-fluorene, alkylcyclohexylene bisphenol, pair -(Hydroxyphenyl)-diisopropylbenzene, and the core alkylation, nuclear halogenated derivatives and mixtures thereof of the foregoing compounds.

Specific examples of the aforementioned bisphenols are: 4,4'-dihydroxybiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)- 2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, α,α-bis-(4-hydroxyphenyl)-diisopropylbenzene, 2,2-double -(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyl Phenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl 4-hydroxyphenyl)-indole, 2 ,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)- Cyclohexane, α,α-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3,5-dichloro-4- Hydroxyphenyl)-propane, and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane; particularly suitable bisphenols are: 2,2-bis-(4-hydroxybenzene) Propane, which is commonly known as bisphenol A, which can be reacted with phosgene to produce an aromatic polycarbonate, and can also be used as disclosed in Japanese Patent Laid-Open No. Hei 1-158033. The method of pre-polymerizing bisphenols and bishydroxyphenyl carbonate monomers into low molecular weight polymers, and then Process for the crystallization of the solid state polymerization (solid polymerization) to give a polycarbonate resin.

In one aspect of the resin composition of the present invention, the thermoplastic resin may comprise a polystyrene-based graft copolymer resin and a polycarbonate resin. Further, the content of the polystyrene-based graft copolymer resin is 5 to 15 parts by weight, and the content of the polycarbonate resin is 55 to 65 parts by weight based on 100 parts by weight of the total weight of the resin composition.

In the present invention, the range of the Izod impact strength of the resin composition is preferably 70 to 86 J/m; and the range of the heat transfer coefficient of the resin composition is preferably 1.3 to 1.35 W/m*K.

In order to obtain the resin composition of the present invention, the mixing method is representative: after dry mixing by a generally used Hanschel mixer, and then a mixer such as an extrusion mixer, a kneader or a Banbury mixer. Melt and mix.

The resin composition of the present invention is suitably used in a molding method such as an injection molding method, an extrusion molding method, a compression molding method, a blow molding method, a thermoforming method, a vacuum molding method, and a hollow molding method.

The resin composition of the present invention may be added with other additives as needed, for example, an antioxidant, a plasticizer, a processing aid, an ultraviolet stabilizer, a UV absorber, a filler, a strengthening agent, a colorant, a slip agent, and a charge prevention agent. The flame retardant, the flame retardant, the heat stabilizer, the coupling agent or other additives may be added during the polymerization reaction, after the polymerization reaction, before the coagulation or during the kneading.

The corresponding model numbers and specifications of the raw material codes used in the following examples and comparative examples of the present invention are as follows:

(A-1): Scale-type graphite - average particle size 300~400 μm, manufactured by Runyou Company, product model +590, hereinafter referred to as graphite +590.

(A-2): Scale-type graphite - average particle size 30 ~ 40 μm, manufactured by Runyou Company, product model -399, hereinafter referred to as graphite-399.

(A-3): Carbon fiber - cut length 6 ± 1 mm, manufactured by Formosa Plastics Co., Ltd., model number CS-2516.

(B-1): Methyl methacrylate-butadiene-styrene graft copolymer - manufactured by Formosa Plastics Co., Ltd., model number FORMORON M-51, hereinafter referred to as MBS.

(C-1): Polycarbonate resin - manufactured by Chi Mei Industrial Co., Ltd., model number WONDERLITE PC-115, hereinafter referred to as PC (granular).

[Example 1]

65 parts by weight of PC particles (C-1), 17.5 parts by weight of flaky graphite (A-1) having an average particle diameter of 300 to 400 μm, and 2.5 parts by weight of flaky graphite having an average particle diameter of 30 to 40 μm ( A-2), 5 parts by weight of carbon fibers (A-3) having a cut length of 6 ± 1 mm, and 10 parts by weight of MBS (B-1), which are the above (C-1), (A-1), A-2), (A-3), and (B-1) materials are dry-mixed by a mixer, and then fed to a two-axis extruder by a loss-in-weight feeder (German W & PZSK-25, barrel temperature) Set 250~280 °C, with exhaust port), after extrusion, and then cut to obtain resin composition particles. Next, the above resin composition particles were shaped to prepare a sample (thickness 3.2 mm) and various physical properties thereof were measured, and the results are shown in Table 1.

The weight ratio of the flaky graphite having an average particle diameter of 30 μm to 40 μm to the flaky graphite having an average particle diameter of 300 μm to 400 μm may be, for example, 1:5 to 1:7, and is about 1 in this embodiment. :7.

Among them, the test conditions are as follows:

I. Izod impact strength (IZOD) measurement: tested according to ASTM D-256 (1/8 inch test piece), expressed in J/m.

2. Determination of heat transfer coefficient: tested according to ASTM E1461 (test piece thickness 3.2 mm), expressed in W/m*K.

[Example 2-3]

The resin composition particles of Example 2-3 were prepared in the same manner as in Example 1 except that the formulation shown in Table 1 was required. The resin composition particles of Example 2-3 were shaped to prepare a sample and various physical properties thereof were measured, and the results are shown in Table 1 (test conditions are as described above).

[Comparative Example 1-3]

The resin composition particles of Comparative Example 1-3 were prepared in the same manner as in Example 1 except that the formulation shown in Table 1 was required. The resin composition particles of Comparative Example 1-3 were shaped to prepare a sample and various physical properties thereof were measured, and the results are shown in Table 1 (test conditions are as described above).

It can be seen from the experimental results of Table 1 that the samples prepared by the resin compositions of Examples 1 to 3 have high Izod impact strength (all above 70 J/m) and also maintain a high heat transfer coefficient. (all are 1.32 W/m*K or more). Therefore, it was confirmed that the resin composition of the present invention can indeed improve the impact strength and achieve the object of the present invention.

In summary, the sample prepared by the resin composition of the present invention after being extruded and injected can have excellent Izod impact strength (test results are all higher than 70 J/m), and high heat conduction is also maintained. Coefficient (experimental results were measured to be 1.32 W/m*K or more). Therefore, the improved formulation of the resin composition of the present invention can increase the service life of the sample and maintain a high heat transfer coefficient, thereby improving its commercial value.

In addition, the present invention can achieve the effect of improving the impact strength by simultaneously using two kinds of flaky graphite of different particle diameters in the resin composition, while maintaining excellent heat conduction characteristics, which is not possessed by the prior art. Unique features.

The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.

Claims (13)

A resin composition comprising: a thermoplastic resin; a scaly graphite; and a carbon fiber. The resin composition according to claim 1, wherein the scaly type graphite comprises at least two kinds of flaky graphite having a particle size. The resin composition according to the first aspect of the invention, wherein the flaky graphite type comprises: flaky graphite having an average particle diameter of 30 μm to 40 μm; and flaky graphite having an average particle diameter of 300 μm to 400 μm. The resin composition according to claim 3, wherein the weight ratio of the flaky graphite having an average particle diameter of 30 μm to 40 μm to the flaky graphite having an average particle diameter of 300 μm to 400 μm is 1:5~ 1:7. The resin composition according to claim 1, wherein the carbon fiber is contained in an amount of from 3 to 13 parts by weight based on 100 parts by total of the total of the resin composition. The resin composition according to claim 1, wherein the carbon fiber is contained in an amount of 5 to 12 parts by weight based on 100 parts by weight of the total of the resin composition. The resin composition according to claim 1, wherein the thermoplastic resin is contained in an amount of 65 to 75 parts by weight based on 100 parts by weight of the total of the resin composition, and the flaky graphite content is 20 parts by weight. ~30 parts by weight, and the content of the carbon fibers is 3 to 13 parts by weight. The resin composition according to claim 1, wherein the thermoplastic resin comprises at least one selected from the group consisting of polystyrene-based graft copolymer resins and polycarbonate resins. The resin composition according to claim 8, wherein the polystyrene-based graft copolymer resin is selected from the group consisting of methyl methacrylate-conjugated diene rubber-styrene graft copolymer, and Styrene-conjugated diene rubber-acrylonitrile-based graft copolymer. The resin composition according to claim 1, wherein the thermoplastic resin comprises a polystyrene-based graft copolymer resin and a polycarbonate resin, and the total weight of the resin composition is 100 parts by weight. The content of the polystyrene-based graft copolymer resin is 5 to 15 parts by weight, and the content of the polycarbonate resin is 55 to 65 parts by weight. The resin composition according to claim 1, wherein the carbon fiber has a length of 3 to 9 mm. The resin composition according to claim 1, wherein the resin composition has an Izod impact strength in the range of 70 to 86 J/m. The resin composition according to claim 1, wherein the heat transfer coefficient of the resin composition ranges from 1.3 to 1.35 W/m*K.