Thermoplastic resin composition

Abstract

To provide a thermoplastic resin composition with excellent rigidity and impact resistance. [Solution] The thermoplastic resin composition comprises a thermoplastic resin, an inorganic reinforcing material, and an acid-modified polyolefin wax. The acid-modified polyolefin wax has carboxyl groups and / or acid anhydride groups thereof. The thermoplastic resin content is 60 parts by mass or more and 95 parts by mass or less per 100 parts by mass of the total amount of the thermoplastic resin and inorganic reinforcing material, the inorganic reinforcing material content is 5 parts by mass or more and 40 parts by mass or less, and the acid-modified polyolefin wax content is 0.02 parts by mass or more and 5.00 parts by mass or less. The density of the acid-modified polyolefin wax is 950 kg / m³. 3 More than 1000kg / m 3 The following conditions apply: Its melting point is between 110°C and 145°C. Its weight-average molecular weight (Mw) is between 2000 and 20000. Its acid value is between 20 mg KOH / g and 100 mg KOH / g.

Description

[Technical Field]

[0001] This invention relates to thermoplastic resin compositions. [Background technology]

[0002] Conventionally, thermoplastic resin compositions containing inorganic reinforcing materials have been blended with acid-modified polyolefin wax in order to improve the impact resistance of molded articles obtained using this thermoplastic resin composition.

[0003] Examples of such thermoplastic resin compositions include aromatic polycarbonate resin, glass fiber, and acid-modified polyethylene wax (high wax 1105A, density 940 kg / m³). 3 A molding resin composition containing (melting point 104°C) has been proposed (for example, Example 1 of Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication 2014 / 208071 Brochure [Overview of the project] [Problems that the invention aims to solve]

[0005] On the other hand, when an acid-modified polyolefin wax is added to a thermoplastic resin composition containing an inorganic reinforcing material, there is a drawback in that the rigidity of the molded product obtained using this thermoplastic resin composition decreases.

[0006] The present invention provides a thermoplastic resin composition that exhibits excellent rigidity and impact resistance. [Means for solving the problem]

[0007] The present invention [1] includes a thermoplastic resin, an inorganic reinforcing material, and an acid-modified polyolefin wax. The acid-modified polyolefin wax has a carboxyl group and / or its acid anhydride group. The content ratio of the thermoplastic resin is 60 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the total amount of the thermoplastic resin and the inorganic reinforcing material. The content ratio of the inorganic reinforcing material is 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the thermoplastic resin and the inorganic reinforcing material. The content ratio of the acid-modified polyolefin wax is 0.02 parts by mass or more and 5.00 parts by mass or less with respect to 100 parts by mass of the total amount of the thermoplastic resin and the inorganic reinforcing material. The density of the acid-modified polyolefin wax is 950 kg / m 3 or more and 1000 kg / m 3 or less. The melting point of the acid-modified polyolefin wax is 110°C or more and 145°C or less. The weight average molecular weight (Mw) of the acid-modified polyolefin wax is 2000 or more and 20000 or less. The acid value of the acid-modified polyolefin wax is 20 mgKOH / g or more and 100 mgKOH / g or less. It is a thermoplastic resin composition.

[0008] The present invention [2] includes the thermoplastic resin composition according to [1] above, wherein the thermoplastic resin is at least one selected from the group consisting of a polycarbonate resin, a polyester resin, a polyacetal resin, a polyamide resin, a polyphenylene oxide resin, and a polyimide resin.

[0009] The present invention [3] includes the thermoplastic resin composition according to [2] above, wherein the thermoplastic resin is a polycarbonate resin. [[ID=​​​​​​The present invention [5] includes the thermoplastic resin composition according to any one of [1] to [4] above, wherein the polyolefin wax in the acid-modified polyolefin wax is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin.

Advantages of the Invention

[0012] The thermoplastic resin composition of the present invention contains an acid-modified polyolefin wax at a predetermined ratio. The density of the acid-modified polyolefin wax is 950 kg / m 3 or more and 1000 kg / m 3 or less, the melting point of the acid-modified polyolefin wax is 110°C or more and 145°C or less, the weight average molecular weight (Mw) of the acid-modified polyolefin wax is 2000 or more and 20000 or less, and the acid value of the acid-modified polyolefin wax is 20 mgKOH / g or more and 100 mgKOH / g or less. Therefore, in the molded product obtained using this thermoplastic resin composition, the rigidity and impact resistance can be improved.

Embodiments for Carrying Out the Invention

[0013] The thermoplastic resin composition contains a thermoplastic resin, an inorganic reinforcing material, and an acid-modified polyolefin wax.

[0014] <Thermoplastic Resin> Examples of the thermoplastic resin include polycarbonate resin, polyester resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, and polyimide resin. From the viewpoint of moldability, as the thermoplastic resin, preferably, at least one selected from the group consisting of polycarbonate resin, polyester resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, and polyimide resin is selected. From the viewpoint of further improving the moldability, polycarbonate resin is mentioned as the thermoplastic resin.

[0015] The polycarbonate resin is obtained, for example, by the reaction of an aromatic diol and phosgene. Such a polycarbonate resin has an aromatic ring derived from an aromatic diol (hereinafter, a polycarbonate resin having an aromatic ring may be referred to as an aromatic polycarbonate resin).

[0016] Examples of commercially available aromatic polycarbonate resins include the Iupilon series (manufactured by Mitsubishi Engineering-Plastics Corporation).

[0017] The melt flow rate (MVR, 300 °C, 1.2 kg load) of the thermoplastic resin is, for example, 1.0 cm 3 / 10 min to 30.0 cm 3 / 10 min, preferably 5.0 cm 3 / 10 min to 20.0 cm 3 / 10 min, more preferably 8.0 cm 3 / 10 min to 10.0 cm 3 / 10 min.

[0018] The thermoplastic resin can be used alone or in combination of two or more kinds.

[0019] The content ratio of the thermoplastic resin is 60 to 95 parts by mass, preferably 70 to 94 parts by mass, more preferably 80 to 93 parts by mass, and still more preferably 88 to 92 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the inorganic reinforcing material.

[0020] Specifically, the content ratio of the thermoplastic resin is, for example, 60 parts by mass or more, preferably 70 parts by mass or more, more preferably 8 parts by mass or more, still more preferably 88 parts by mass or more, and 95 parts by mass or less, preferably 94 parts by mass or less, more preferably 93 parts by mass or less, and still more preferably 92 parts by mass or less with respect to 100 parts by mass of the total amount of the thermoplastic resin and the inorganic reinforcing material.

[0021] If the content ratio of the thermoplastic resin is at least the above lower limit, the moldability can be improved.

[0022] On the other hand, if the content of thermoplastic resin is below the lower limit mentioned above, the moldability will decrease.

[0023] Furthermore, if the content of thermoplastic resin is below the above upper limit, the rigidity (specifically, bending strength, hardness, and so on) and heat resistance can be improved.

[0024] On the other hand, if the content of thermoplastic resin exceeds the above upper limit, the rigidity and heat resistance will decrease.

[0025] The content of the thermoplastic resin is, for example, 60% to 95% by mass, preferably 70% to 94% by mass, and more preferably 80% to 93 parts by mass, relative to the thermoplastic resin composition.

[0026] <Inorganic reinforcement> Inorganic reinforcing materials provide rigidity and heat resistance.

[0027] Examples of inorganic reinforcing materials include glass reinforcing materials, carbon reinforcing materials, and other reinforcing materials.

[0028] Examples of glass reinforcing materials include glass fibers, glass flakes, and glass powder. From the viewpoint of rigidity and heat resistance, glass fibers and glass flakes are preferred as glass reinforcing materials.

[0029] The shape of the glass fibers is not particularly limited. Examples of glass fiber shapes include roving-like and strand-like forms.

[0030] The length of the glass fibers is, for example, 0.5 mm to 20.0 mm, preferably 1.0 mm to 10.0 mm, and more preferably 2.0 mm to 5.0 mm.

[0031] More specifically, the length of the glass fibers is, for example, 0.5 mm or more, preferably 1.0 mm or more, and more preferably 2.0 mm or more, from the viewpoint of rigidity, and from the viewpoint of handling, for example, 20.0 mm or less, preferably 10.0 mm or less, and more preferably 5.0 mm or less.

[0032] The glass fibers may be surface-treated, for example, with a surface treatment agent (e.g., a silane coupling agent).

[0033] Examples of carbon reinforcing materials include carbon fibers and carbon particles. From the viewpoint of rigidity and heat resistance, carbon fibers are preferred as the carbon reinforcing material.

[0034] The shape and length of the carbon fibers are the same as those of the glass fibers described above.

[0035] Furthermore, the carbon fibers may be surface-treated, for example, with a surface treatment agent (e.g., a silane coupling agent).

[0036] Other reinforcing materials include, for example, oxides, hydroxides (e.g., aluminum hydroxide), carbonates, sulfates, and carbonates (preferably calcium carbonate).

[0037] From the viewpoint of rigidity and heat resistance, glass reinforcement materials and carbon reinforcement materials are preferred as inorganic reinforcement materials. The inorganic reinforcement material is more preferably a glass reinforcement material and / or a carbon reinforcement material. The inorganic reinforcement material is even more preferably a glass reinforcement material.

[0038] Inorganic reinforcing materials can be used alone or in combination of two or more types.

[0039] The inorganic reinforcing material content is 5 to 40 parts by mass, preferably 6 to 30 parts by mass, more preferably 7 to 20 parts by mass, and even more preferably 8 to 12 parts by mass, based on 100 parts by mass of the total amount of thermoplastic resin and inorganic reinforcing material.

[0040] More specifically, the inorganic reinforcing material content is 5 parts by mass or more, preferably 6 parts by mass or more, more preferably 7 parts by mass or more, even more preferably 8 parts by mass or more, and 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 12 parts by mass or less, based on 100 parts by mass of the total amount of thermoplastic resin and inorganic reinforcing material.

[0041] If the content of inorganic reinforcing materials is above the lower limit mentioned above, rigidity and heat resistance can be improved.

[0042] On the other hand, if the content of inorganic reinforcing materials is below the above lower limit, the rigidity and heat resistance will decrease.

[0043] Furthermore, if the content of inorganic reinforcing materials is below the above upper limit, moldability can be improved.

[0044] On the other hand, if the proportion of inorganic reinforcing material exceeds the above upper limit, the moldability decreases.

[0045] The inorganic reinforcing material content is, for example, 5% to 40% by mass, preferably 6% to 30% by mass, and more preferably 7% to 20% by mass, relative to the thermoplastic resin composition.

[0046] <Acid-modified polyolefin wax> Acid-modified polyolefin wax provides impact resistance.

[0047] Acid-modified polyolefin wax is an acid-modified product of polyolefin wax (unmodified wax).

[0048] Polyolefin waxes contain constituent units derived from olefins. Such polyolefin waxes are polymers of olefins.

[0049] Examples of olefins include ethylene and α-olefins.

[0050] Examples of α-olefins include α-olefins having 3 or more carbon atoms. Examples of α-olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene. More preferably, the olefin is ethylene alone, or ethylene and α-olefin in combination. In other words, more preferably, the polyolefin wax in acid-modified polyolefin wax is a homopolymer of ethylene or a copolymer of ethylene and α-olefin. Even more preferably, the olefin is ethylene. In other words, even more preferably, the polyolefin wax in acid-modified polyolefin wax is a homopolymer of ethylene.

[0051] Olefins can be used alone or in combination of two or more types. Furthermore, monomers derived from fossil fuels and / or biomass can be used as olefins. Specifically, the choice of olefin can be between the sole use of fossil fuel-derived monomers, the sole use of biomass-derived monomers, or a combination of fossil fuel-derived and biomass-derived monomers. Fossil fuels include petroleum, coal, natural gas, shale gas, or combinations thereof. Biomass refers to all renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, whether plant-derived or animal-derived.

[0052] Polyolefin waxes are obtained by polymerizing olefins in the presence of an olefin polymerization catalyst (Ziegler-Natta catalyst).

[0053] The density of polyolefin wax is, for example, 945 kg / m³. 3 ~985 kg / m 3 Preferably, 950 kg / m 3 ~983 kg / m 3 , comfortably, 960 kg / m 3 ~982 kg / m 3 That is the case.

[0054] For more details, the density of polyolefin wax is, for example, 945 kg / m³. 3 Preferably, 950 kg / m 3 In summary, the comfortable rate is 960 kg / m³. 3 In addition, for example, 985 kg / m 3 Preferably, 983 kg / m 3 More preferably, 982 kg / m 3 The following applies:

[0055] If the density of the polyolefin wax is within the above range, the density of the acid-modified polyolefin wax, described later, can be adjusted to a predetermined range.

[0056] The above density can be measured using a density gradient tube in accordance with JIS K7112 (the same applies hereafter).

[0057] The melting point of polyolefin wax is, for example, 110°C to 145°C, preferably 115°C to 140°C.

[0058] More specifically, the melting point of polyolefin wax is, for example, 110°C or higher, preferably 115°C or higher, and for example, 145°C or lower, preferably 140°C or lower.

[0059] If the melting point of the polyolefin wax is within the above range, the melting point of the acid-modified polyolefin wax, described later, can be adjusted to a predetermined range.

[0060] The method for measuring the melting point will be described in detail in the examples below (the same applies hereafter).

[0061] The weight-average molecular weight (Mw) of the polyolefin wax is, for example, 1,000 to 18,000, preferably 2,000 to 15,000, more preferably 2,500 to 12,000, even more preferably 4,000 to 10,000, and particularly preferably 5,000 to 7,000.

[0062] If the weight-average molecular weight (Mw) of the polyolefin wax is within the above range, the weight-average molecular weight (Mw) of the acid-modified polyolefin wax described later can be adjusted to a predetermined range.

[0063] The weight-average molecular weight (Mw) mentioned above is the polystyrene-equivalent molecular weight obtained by gel permeation chromatography (GPC) (the same applies hereafter).

[0064] Acid-modified polyolefin wax is obtained by modifying polyolefin wax with an unsaturated carboxylic acid.

[0065] Examples of unsaturated carboxylic acids include those having 3 to 8 carbon atoms. Examples of unsaturated carboxylic acids having 3 to 8 carbon atoms include monobasic acids and dibasic acids. Examples of monobasic acids include (meth)acrylic acid (acrylic acid and / or methacrylic acid), crotonic acid, and isocrotonic acid. Examples of dibasic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, allylsuccinic acid, nadic acid, methylnadic acid, tetrahydrofumaric acid, and methylhexahydrophthalic acid.

[0066] Furthermore, unsaturated carboxylic acids include the acid anhydrides of the unsaturated carboxylic acids mentioned above.

[0067] Preferably, unsaturated carboxylic acids include acid anhydrides of unsaturated carboxylic acids. More preferably, unsaturated carboxylic acids include acid anhydrides of dibasic acids. Even more preferably, unsaturated carboxylic acids include maleic anhydride.

[0068] Unsaturated carboxylic acids can be used alone or in combination of two or more types.

[0069] Acid-modified polyolefin wax is obtained by reacting the above-mentioned polyolefin wax with an unsaturated carboxylic acid. In this reaction, the unsaturated carboxylic acid grafts onto the polyolefin wax.

[0070] Specifically, first, the polyolefin wax is melted at, for example, 100°C or higher, preferably 150°C or higher, and for example, 180°C or lower.

[0071] Next, the unsaturated carboxylic acid and radical polymerization initiator are added, and the mixture is heated and stirred.

[0072] The proportion of unsaturated carboxylic acid is, for example, 1 to 15 parts by mass, preferably 4 to 10 parts by mass, and more preferably 6 to 8 parts by mass, per 100 parts by mass of polyolefin wax.

[0073] Examples of radical polymerization initiators include organic peroxides (e.g., di-tert-butyl peroxide).

[0074] The blending ratio of the radical polymerization initiator is, for example, 0.5 to 5.0 parts by mass, preferably 1.0 to 2.0 parts by mass, per 100 parts by mass of polyolefin wax.

[0075] Radical polymerization initiators can be used alone or in combination of two or more types.

[0076] The heating conditions include a heating temperature of, for example, 100°C to 200°C, preferably 150°C to 180°C. The heating time is, for example, 0.5 hours to 6.0 hours.

[0077] This process produces an acid-modified polyolefin wax. Such an acid-modified polyolefin wax has carboxyl groups derived from an unsaturated carboxylic acid and / or acid anhydride groups derived from an acid anhydride of an unsaturated carboxylic acid.

[0078] The density of acid-modified polyolefin wax is 950 kg / m³. 3 ~1000kg / m 3 Preferably, 960 kg / m 3 ~990 kg / m 3 , more comfortably, 970 kg / m 3 ~980 kg / m 3 That is the case.

[0079] For more details, the density of acid-modified polyolefin wax is 950 kg / m³. 3 Preferably, 960 kg / m 3 In summary, a comfortable 970 kg / m³ 3 In addition, 1000 kg / m 3 Preferably, 990 kg / m 3 More preferably, 980 kg / m 3 The following applies:

[0080] If the density of the acid-modified polyolefin wax is above the lower limit mentioned above, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0081] On the other hand, if the density of the acid-modified polyolefin wax is below the lower limit mentioned above, the decrease in rigidity cannot be suppressed. Therefore, it is not possible to achieve both rigidity and impact resistance.

[0082] Furthermore, if the density of the acid-modified polyolefin wax is below the above upper limit, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0083] On the other hand, if the density of the acid-modified polyolefin wax exceeds the above upper limit, the decrease in impact resistance cannot be suppressed. Therefore, it is not possible to achieve both rigidity and impact resistance.

[0084] The melting point of the acid-modified polyolefin wax is 110°C to 145°C, preferably 115°C to 140°C, more preferably 116°C to 135°C, even more preferably 117°C to 130°C, and most preferably 118°C to 122°C.

[0085] More specifically, the melting point of the acid-modified polyolefin wax is 110°C or higher, preferably 115°C or higher, more preferably 116°C or higher, even more preferably 117°C or higher, particularly preferably 118°C or higher, and 145°C or lower, preferably 140°C or lower, more preferably 135°C or lower, even more preferably 130°C or lower, particularly preferably 122°C or lower.

[0086] If the melting point of the acid-modified polyolefin wax is above the lower limit mentioned above, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0087] On the other hand, if the melting point of the acid-modified polyolefin wax is below the lower limit mentioned above, the decrease in rigidity cannot be suppressed. Therefore, it is not possible to achieve both rigidity and impact resistance.

[0088] Furthermore, if the melting point of the acid-modified polyolefin wax is below the above upper limit, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0089] On the other hand, if the melting point of the acid-modified polyolefin wax exceeds the above upper limit, the decrease in impact resistance cannot be suppressed. Therefore, it is not possible to achieve both rigidity and impact resistance.

[0090] The weight-average molecular weight (Mw) of the acid-modified polyolefin wax is 2000 to 20000, preferably 2500 to 16000, more preferably 3000 to 14000, even more preferably 5000 to 11000, and particularly preferably 6000 to 9000.

[0091] The weight-average molecular weight (Mw) of the acid-modified polyolefin wax is 2000 or more, preferably 2500 or more, more preferably 3000 or more, even more preferably 5000 or more, particularly preferably 6000 or more, and also 20000 or less, preferably 16000 or less, more preferably 14000 or less, even more preferably 11000 or less, and particularly preferably 9000 or less.

[0092] If the weight-average molecular weight (Mw) of the acid-modified polyolefin wax is above the lower limit mentioned above, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0093] On the other hand, if the weight-average molecular weight (Mw) of the acid-modified polyolefin wax is below the lower limit mentioned above, the density and melting point will decrease significantly, and the decrease in rigidity cannot be suppressed. Therefore, it is not possible to achieve both rigidity and impact resistance.

[0094] Furthermore, if the weight-average molecular weight (Mw) of the acid-modified polyolefin wax is below the above upper limit, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0095] On the other hand, if the weight-average molecular weight (Mw) of the acid-modified polyolefin wax exceeds the above upper limit, it becomes less reactive with the inorganic reinforcing material, and the effect of improving impact resistance is reduced. Therefore, it is not possible to achieve both rigidity and impact resistance.

[0096] The acid value of the acid-modified polyolefin wax is 20 mg KOH / g to 100 mg KOH / g, preferably 25 mg KOH / g to 80 mg KOH / g, more preferably 30 mg KOH / g to 60 mg KOH / g, even more preferably 40 mg KOH / g to 55 mg KOH / g, and particularly preferably 45 mg KOH / g to 50 mg KOH / g.

[0097] More specifically, the acid value of the acid-modified polyolefin wax is 20 mg KOH / g or more, preferably 25 mg KOH / g or more, more preferably 30 mg KOH / g or more, even more preferably 40 mg KOH / g or more, particularly preferably 45 mg KOH / g or more, and 100 mg KOH / g or less, preferably 80 mg KOH / g or less, more preferably 60 mg KOH / g or less, even more preferably 55 mg KOH / g or less, particularly preferably 50 mg KOH / g or less.

[0098] If the acid value of the acid-modified polyolefin wax is above the lower limit mentioned above, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0099] On the other hand, if the acid value of the acid-modified polyolefin wax is below the lower limit mentioned above, it is not possible to improve impact resistance. Therefore, it is not possible to achieve both rigidity and impact resistance.

[0100] Furthermore, if the acid value of the acid-modified polyolefin wax is below the above upper limit, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0101] On the other hand, if the acid value of the acid-modified polyolefin wax exceeds the above upper limit, the degree of crystallinity and melting point of the acid-modified polyolefin wax decrease, and the decrease in rigidity cannot be suppressed. Therefore, it is not possible to achieve both rigidity and impact resistance.

[0102] The above acid value can be measured in accordance with JIS K5902.

[0103] Acid-modified polyolefin waxes can be used alone or in combination of two or more types.

[0104] The content of the acid-modified polyolefin wax is 0.02 parts by mass to 5.00 parts by mass, preferably 0.10 parts by mass to 3.00 parts by mass, more preferably 0.50 parts by mass to 2.00 parts by mass, and even more preferably 0.80 parts by mass to 1.50 parts by mass, per 100 parts by mass of the total amount of thermoplastic resin and inorganic reinforcing material.

[0105] More specifically, the content of acid-modified polyolefin wax is 0.02 parts by mass or more, preferably 0.10 parts by mass or more, more preferably 0.50 parts by mass or more, even more preferably 0.80 parts by mass or more, and 5.00 parts by mass or less, preferably 3.00 parts by mass or less, more preferably 2.00 parts by mass or less, and even more preferably 1.50 parts by mass or less.

[0106] If the content of acid-modified polyolefin wax is above the lower limit mentioned above, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0107] On the other hand, if the content of acid-modified polyolefin wax is below the lower limit mentioned above, the impact resistance will decrease.

[0108] Furthermore, if the content of acid-modified polyolefin wax is below the above upper limit, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0109] On the other hand, if the content of acid-modified polyolefin wax exceeds the above upper limit, the decrease in rigidity cannot be suppressed. Therefore, it is not possible to achieve both rigidity and impact resistance.

[0110] Based on the above, by adjusting the density, melting point, weight-average molecular weight (Mw), acid value, and content ratio of the acid-modified polyolefin wax to the above range, impact resistance can be improved while suppressing a decrease in rigidity. As a result, both rigidity and impact resistance can be achieved.

[0111] <Other polymers> The thermoplastic resin composition may contain other polymers as needed, from the viewpoint of improving the surface smoothness of the molded product (described later).

[0112] Other polymers include at least one selected from the group consisting of structural units derived from aromatic vinyl compounds, structural units derived from cyano group-containing vinyl compounds, structural units derived from (meth)acrylic acid esters, structural units derived from diene compounds, and structural units derived from organosiloxanes.

[0113] Examples of aromatic vinyl compounds include styrene and α-methylstyrene.

[0114] Examples of cyano group-containing vinyl compounds include (meth)acrylonitrile.

[0115] Examples of (meth)acrylic acid esters include methyl (meth)acrylate and ethyl (meth)acrylate.

[0116] Examples of diene compounds include butadiene and isoprene.

[0117] Examples of organosiloxanes include polydimethylsiloxane.

[0118] Other polymers of this kind include, specifically, acrylonitrile-butadiene-styrene copolymer (ABS), methyl methacrylate-butadiene-styrene copolymer (MBS), alkyl methacrylate-styrene copolymer (MS), alkyl methacrylate-polydimethylsiloxane-styrene copolymer, acrylonitrile-butadiene rubber (NBR), styrene-butadiene copolymer (SBR), and hydrogenated styrene-butadiene-styrene copolymer (SEBS). Among other polymers, methyl methacrylate-butadiene-styrene copolymer is particularly preferred.

[0119] The melt flow rate (MFR, 200°C, 5kg load) of other polymers is, for example, 0.1kg / 10min to 20kg / 10min, preferably 0.2kg / 10min to 5kg / 10min, and more preferably 0.3kg / 10min to 1kg / 10min.

[0120] The density of other polymers is, for example, 900 kg / m³. 3 ~1200kg / m 3 Preferably, 920 kg / m 3 ~1100kg / m 3 More preferably, 940 kg / m 3 ~1000kg / m 3 That is the case.

[0121] The glass transition temperatures of other polymers are, for example, -140°C to 0°C, preferably -100°C to -60°C.

[0122] Other polymers can be used alone or in combination of two or more types.

[0123] The content of other polymers is, for example, 1 to 10 parts by mass, preferably 2 to 7 parts by mass, and more preferably 4 to 6 parts by mass, per 100 parts by mass of the total amount of thermoplastic resin and inorganic reinforcing material.

[0124] More specifically, the content of other polymers is, for example, 1 part by mass or more, preferably 2 parts by mass or more, per 100 parts by mass of the total amount of thermoplastic resin and inorganic reinforcing material, from the viewpoint of surface smoothness of the molded product (described later), more preferably 4 parts by mass or more, from the viewpoint of suppressing contamination during molding (contamination presumed to originate from low molecular weight components and low crystalline components contained in acid-modified polyolefin wax, or by-products during the production of acid-modified polyolefin wax), and from the viewpoint of suppressing a decrease in rigidity, for example 10 parts by mass or less, preferably 7 parts by mass or less, more preferably 6 parts by mass or less.

[0125] <Additives> The thermoplastic resin composition may contain additives in predetermined proportions as needed.

[0126] Examples of additives include flame retardants, flame retardant enhancers, heat stabilizers, antioxidants, heat-resistant agents, weather-resistant agents, light stabilizers, mold release agents, flow modifiers, colorants, antistatic agents, crystal nucleating agents, plasticizers, foaming agents, and softeners.

[0127] Additives can be used individually or in combination of two or more types.

[0128] <Method for producing thermoplastic resin compositions> A thermoplastic resin composition is obtained by melt-kneading a thermoplastic resin, an inorganic reinforcing material, an acid-modified polyolefin wax, other polymers as needed, and additives as needed. The thermoplastic resin composition can then be used to produce molded articles, for example, by injection molding under known conditions.

[0129] <Effects and Effects> The thermoplastic resin composition contains acid-modified polyolefin wax in a predetermined proportion. The density of the acid-modified polyolefin wax is 950 kg / m³. 3 More than 1000kg / m 3 The following conditions apply to the acid-modified polyolefin wax: the melting point is between 110°C and 145°C; the weight-average molecular weight (Mw) is between 2000 and 20000; and the acid value is between 20 mg KOH / g and 100 mg KOH / g. Therefore, the rigidity and impact resistance of molded articles obtained using this thermoplastic resin composition can be improved.

[0130] More specifically, the thermoplastic resin composition containing the inorganic reinforcing material is blended with acid-modified polyolefin wax to improve impact resistance.

[0131] On the other hand, when acid-modified polyolefin wax is added to a thermoplastic resin composition containing inorganic reinforcing materials, a drawback arises: the rigidity decreases. In other words, when acid-modified polyolefin wax is added to a thermoplastic resin composition containing inorganic reinforcing materials, impact resistance improves, but rigidity decreases.

[0132] In contrast, the thermoplastic resin composition contains an acid-modified polyolefin wax having a predetermined density, a predetermined melting point, a predetermined weight-average molecular weight (Mw), and a predetermined acid value in a predetermined proportion. Therefore, it is possible to improve impact resistance while suppressing a decrease in rigidity. As a result, it is possible to achieve both rigidity and impact resistance. [Examples]

[0133] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, specific numerical values ​​such as blending ratios (content), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than") of the blending ratios (content), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above.

[0134] <Details of ingredients> Polyethylene wax 1: Ethylene homopolymer, weight-average molecular weight 2600, density 950 kg / m³ 3 Melting point 116℃, product name "High Wax 100P", manufactured by Mitsui Chemicals, Inc. Polyethylene wax 2: Ethylene homopolymer, weight-average molecular weight 6700, density 970 kg / m³ 3 Melting point 122℃, product name "High Wax 200P", manufactured by Mitsui Chemicals, Inc. Aromatic polycarbonate: MVR (300℃, 1.2kg) = 9.0cm³ / 10min, product name "Yupilon S-2000F", manufactured by Mitsubishi Engineering Plastics Corporation. Glass fiber: Chopped strand CS(F)3PE-455S, fiber length 3mm, manufactured by Nitto Boseki Co., Ltd. 1105A: Maleic anhydride-modified ethylene-propylene copolymer, density 940 kg / m³ 3Melting point 104℃, weight-average molecular weight 4400, acid value 60 mgKOH / g, product name "High Wax 1105A", manufactured by Mitsui Chemicals, Inc.

[0135] <Manufacturing of acid-modified polyolefin wax> Manufacturing Example 1 1800g of polyethylene wax was placed in a glass reactor and melted at 160°C under a nitrogen atmosphere. Next, 52.6g of maleic anhydride and 11.1g of di-t-butyl peroxide were continuously supplied at 160°C over 3 hours. After heating for 1 hour, the molten state was degassed in a 10mmHg vacuum for 0.5 hours to remove volatile components, and then cooled. This produced acid-modified polyolefin wax (maleic anhydride-modified polyethylene wax). The density of the acid-modified polyolefin wax was 966 kg / m³. 3 The melting point of the acid-modified polyolefin wax was 114°C. The weight-average molecular weight of the acid-modified polyolefin wax was 3100. The acid value of the acid-modified polyolefin wax was 43 mgKOH / g.

[0136] Manufacturing Example 2 Acid-modified polyolefin wax (maleic anhydride-modified polyethylene wax) was manufactured using the same procedure as in Manufacturing Example 1. However, polyethylene wax 1 was replaced with polyethylene wax 2. The density of the acid-modified polyolefin wax was 978 kg / m³. 3 The melting point of the acid-modified polyolefin wax was 120°C. The weight-average molecular weight of the acid-modified polyolefin wax was 6800. The acid value of the acid-modified polyolefin wax was 49 mgKOH / g.

[0137] <Manufacturing of thermoplastic resin compositions and molded articles> Example 1 90 parts by mass of aromatic polycarbonate, 10 parts by mass of glass fiber, and 1 mass of acid-modified polyolefin wax from Production Example 1 were melt-kneaded using a co-rotating twin-screw extruder (manufactured by Parker Corporation, φ25 mm, L / D=41) under the conditions of cylinder temperature 280°C, discharge rate 15 kg / hour, and screw rotation speed 180 rpm, and then pelletized. A thermoplastic resin composition was produced by this process.

[0138] Next, the obtained pellets (thermoplastic resin composition) were dried under reduced pressure at 80°C for 10 hours, and then injection molded using an injection molding machine (Niigata Machine Techno Co., Ltd., Niigata NN100) under the following conditions: cylinder temperature 280°C, screw rotation speed 70 rpm, injection pressure 150 MPa, and mold temperature 100°C. Subsequently, a JIS K7139-A1 test piece was injection molded under the following conditions: cylinder temperature 280°C, screw rotation speed 50 rpm, injection pressure 120 MPa, and mold temperature 100°C to produce a molded product (100 mm × 100 mm × 3 mm thick rectangular plate).

[0139] Example 2, Comparative Example 1 and Comparative Example 2 Thermoplastic resin compositions and molded articles were manufactured using the same procedure as in Example 1. However, the formulations of each component were modified based on those shown in Table 1.

[0140] <Rating> [density] The density of the acid-modified polyolefin waxes for each production example was measured using a density gradient tube in accordance with JIS K7112.

[0141] [Melting point] The melting points of acid-modified polyolefin waxes from each manufacturing example were measured. Specifically, using a DSC (X-DSC7000) manufactured by SII, the temperature was raised from -40°C to 200°C at a rate of 10°C / min and held for 10 minutes, then cooled down to -40°C at a rate of 10°C / min and held for 5 minutes, and then raised to 200°C at a rate of 10°C / min. The point with the highest intensity of the melting peak during the second heating was defined as the melting point.

[0142] [Weight average molecular weight (Mw)] The weight-average molecular weight (Mw) of the acid-modified polyolefin waxes in each production example was measured. Specifically, GPC measurements were performed under the following conditions. The weight-average molecular weight (Mw) was also determined by creating a calibration curve using commercially available monodisperse standard polystyrene and calculating it according to the conversion method described below. {conditions} Equipment: Gel permeation chromatograph HLC-8321 GPC / HT type (manufactured by Tosoh Corporation) Solvent: o-dichlorobenzene Columns: TSKgel GMH6-HT x 2, TSKgel GMH6-HTL column x 2 (both manufactured by Tosoh Corporation) Flow rate: 1.0 ml / min Sample: 0.1 mg / mL o-dichlorobenzene solution Column temperature: 140℃ Injection volume: 400μl Detector: Differential refractometer Sampling time interval: 0.5 seconds

[0143] [Acid value] The acid value of the acid-modified polyolefin waxes for each manufacturing example was measured in accordance with JIS K5902.

[0144] [rigidity] (Bending strength) The bending strength of molded articles for each example and comparative example was measured. Specifically, the prepared JIS K7139-A1 test specimens were tested according to JIS K-7171 under the conditions of a test temperature of 23°C, a test speed of 2 mm / min, and a bending span distance of 64 mm, and the bending strength was measured. The results are shown in Table 1.

[0145] (Rockwell hardness) For each example and comparative example, the Rockwell hardness of the molded product (3mm thick square plate) was measured according to ASTM D785, at a test temperature of 23°C, a test load of 60 kgf, with two molded products stacked together, and under L-scale conditions. The results are shown in Table 1.

[0146] [Impact Resistance] (Charpy impact test) Test specimens were prepared for each example and comparative example of the molded product in accordance with JIS K7139-A1. Then, the Charpy impact value was measured in accordance with JIS K-7111 at a test temperature of 23°C with a notch. The results are shown in Table 1.

[0147] [Table 1]

Claims

1. It comprises a thermoplastic resin, an inorganic reinforcing material, and an acid-modified polyolefin wax. The acid-modified polyolefin wax has a carboxyl group and / or its acid anhydride group, The content ratio of the thermoplastic resin is 60 parts by mass or more and 95 parts by mass or less, based on 100 parts by mass of the total amount of the thermoplastic resin and the inorganic reinforcing material. The content ratio of the inorganic reinforcing material is 5 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the total amount of the thermoplastic resin and the inorganic reinforcing material. The content ratio of the acid-modified polyolefin wax is 0.02 parts by mass or more and 5.00 parts by mass or less, based on 100 parts by mass of the total amount of the thermoplastic resin and the inorganic reinforcing material. The density of the acid-modified polyolefin wax is 950 kg / m³. ３ More than 1000kg / m ３ The following: The melting point of the acid-modified polyolefin wax is 110°C or higher and 145°C or lower. The weight-average molecular weight (Mw) of the acid-modified polyolefin wax is 2000 or more and 20000 or less. A thermoplastic resin composition wherein the acid value of the acid-modified polyolefin wax is 20 mg KOH / g or more and 100 mg KOH / g or less.

2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of polycarbonate resin, polyester resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, and polyimide resin.

3. The thermoplastic resin composition according to claim 2, wherein the thermoplastic resin is a polycarbonate resin.

4. The thermoplastic resin composition according to claim 1, wherein the inorganic reinforcing material is a glass reinforcing material and / or a carbon reinforcing material.

5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the polyolefin wax in the acid-modified polyolefin wax is an ethylene homopolymer or a copolymer of ethylene and α-olefin.

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