Polyolefin wax

Abstract

The object of the present invention is to provide a polyolefin wax that provides excellent adhesion to thermoplastic resin compositions. [Solution] A polyolefin wax (X) containing a polyolefin (A) that satisfies the following (1) to (3), wherein the silicon content measured by fluorescent X-rays is 100 to 10,000 ppm. (1) Number of carbon-carbon double bonds per 1,000 carbon atoms: 0.1 to 20 (2) The melt viscosity measured at 160°C using a rotational viscometer is 50 to 50,000 mPa·s (3) The softening point measured by the ring-ball method is 50-160°C

Description

Technical Field

[0001] The present invention relates to polyolefin wax.

Background Art

[0002] Conventionally, polyolefin wax has been used in thermoplastic resin compositions as, for example, a lubricant, a mold release agent, a molding aid, etc. (for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, even with the technology of Patent Document 1 above, the adhesiveness to metals etc. cannot be said to be sufficiently satisfactory, and its solution has been demanded. An object of the present invention is to provide a polyolefin wax that gives excellent adhesiveness to a thermoplastic resin composition.

Means for Solving the Problems

[0005] As a result of investigations to achieve the above object, the present inventors have arrived at the present invention. That is, the present invention is a polyolefin wax (X) containing a polyolefin (A) satisfying the following (1) to (3) and having a silicon content measured by fluorescent X-ray of 100 to 10,000 ppm. (1) The number of carbon-carbon double bonds per 1,000 carbon atoms is 0.1 to 20 (2) The melt viscosity measured at 160 °C using a rotational viscometer is 50 to 50,000 mPa·s (3) The softening point measured by the ring and ball method is 50 to 160 °C

Effects of the Invention

[0006] The polyolefin wax (X) of the present invention provides the following effects. (1) Provides excellent adhesion to thermoplastic resin compositions. (2) Provides thermoplastic resin compositions with excellent antistatic properties. (3) It provides the asphalt mixture with excellent dynamic stability and excellent residual stability, resulting in good workability. [Modes for carrying out the invention]

[0007] <Polyolefin (A)> Examples of monomers (olefin monomers) that constitute polyolefin (A) in the present invention include ethylene, propylene, butene, butadiene, and isoprene. The monomer constituting the polyolefin (A) is preferably at least one selected from the group consisting of ethylene, propylene, butene, butadiene, and isoprene, and more preferably ethylene, propylene, or a combination of ethylene and propylene.

[0008] The polyolefin (A) described above may also contain other monomers in addition to the olefin monomer described above. In that case, based on the total weight of the monomers constituting the polyolefin (A), the weight of the other monomers is preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less. Other monomers include styrene and unsaturated silane compounds (such as vinyltrimethoxysilane).

[0009] The number of double bonds per 1,000 carbon atoms of the above polyolefin (A) [the number of carbon-carbon double bonds at the molecular ends and / or in the molecular chain of polyolefin (A)] is 0.1 to 20, preferably 0.5 to 15, and more preferably 1.0 to 10, from the viewpoint of the productivity and modification effect of the block polymer (X) described later.

[0010] The number of double bonds in polyolefin (A) is1 This can be determined from the 1H-NMR spectrum. Specifically, the peaks in the spectrum are assigned, and the relative values ​​of the number of double bonds in polyolefin (A) and the number of carbon atoms in polyolefin (A) are determined from the integral values ​​derived from the double bonds in polyolefin (A) at 4.5-6 ppm and from polyolefin (A), and the number of double bonds in the molecular ends and / or molecular chains of polyolefin (A) per 1,000 carbon atoms is calculated. The calculation of the number of double bonds in the examples described later followed the above method.

[0011] Examples of methods for producing the above-mentioned polyolefin (A) include the following: (1) A method for thermal depolymerization of high molecular weight (preferably with a number-average molecular weight (Mn) of 60,000 to 1,000,000, more preferably with a Mn of 80,000 to 250,000) polyolefin (A0) (2) A method of polymerizing monomers in the presence of a polymerization catalyst.

[0012] Of the above (1) and (2), (1) is preferable from the standpoint of productivity.

[0013] The thermal reduction method includes (1) a method of heating the above high molecular weight polyolefin (A0) in the absence of organic peroxides, for example at 300-450°C for 0.1-10 hours, and (2) a method of heating in the presence of organic peroxides [e.g., 2,5-dimethyl-2,5-di(t-butylperoxy)hexane], for example at 180-300°C for 0.5-10 hours. Of these, method (1) is preferred from an industrial and productivity standpoint, as it is easier to obtain molecules with a large number of double bonds at the molecular ends and / or in the molecular chain.

[0014] In the above polyolefin (A), the higher the thermal degeneration temperature or the longer the thermal degeneration time in the thermal degeneration process, the greater the number of double bonds per 1,000 carbon atoms tends to be. Furthermore, the smaller the Mn of high molecular weight polyolefin (A0), the higher the thermal degeneration temperature, or the longer the thermal degeneration time, the smaller the Mn of polyolefin (A) tends to be. Incidentally, the polyolefin (A) may be used alone or in combination of two or more.

[0015] The polyolefin (A) in the present invention has a melt viscosity measured at 160 °C using a rotational viscometer of 50 to 50,000 mPa·s, preferably 150 to 20,000 mPa·s, and more preferably 300 to 10,000 mPa·s. Incidentally, the above melt viscosity can be measured with a single cylindrical rotational viscometer (RH-85 type viscometer, manufactured by Toki Sangyo Co., Ltd.). The above melt viscosity can be appropriately adjusted, for example, by the composition of the monomer of (A), the Mn of (A), and the heat degradation process conditions of the high molecular weight polyolefin (A0).

[0016] The polyolefin (A) in the present invention has a softening point measured by the ring and ball method of 50 to 160 °C, preferably 70 to 140 °C, and more preferably 90 to 120 °C. The above softening point can be appropriately adjusted, for example, by the composition of the monomer of (A), the Mn of (A), and the heat degradation process conditions of the high molecular weight polyolefin (A0). The softening point in the present invention can be measured under the following conditions in accordance with JIS K2207. · Automatic softening point measuring device "ASP-MG", manufactured by Matech Co., Ltd. · Heating rate: 10 °C / min · Solvent: glycerin

[0017] Examples of the polyolefin (A) in the present invention include polyolefin (A1), silane-modified polyolefin (A2), and silane-crosslinked polyolefin (A3). Incidentally, (A1) can be distinguished from (A2) and (A3) by the presence or absence of the unsaturated silane compound which is the above constitutional monomer.

[0018] Examples of the above high molecular weight polyolefin (A0) include (A01), (A02), and (A03). (A01): For example, polyethylene, polypropylene, ethylene / propylene copolymer. An example of a commercially available product as described above (A01) is the product "Novatec LD LJ902" manufactured by Nippon Polyethylene Co., Ltd. (A02): Silane-modified polyolefin (for example, polyethylene modified with an unsaturated silane compound). An example of a commercially available product as described in (A02) above is the product name "Linkron XPM-800H" manufactured by Mitsubishi Chemical Corporation. (A03): Silane-crosslinked polyolefin (for example, a silane-modified polyolefin that has been crosslinked). Examples of the above (A03) include wire insulation materials and used wire insulation materials.

[0019] <Polyolefin wax (X)> The polyolefin wax (X) of the present invention contains a polyolefin (A) that satisfies the following conditions (1) to (3), and has a silicon content of 100 to 10,000 ppm as measured by fluorescent X-rays. (1) Number of carbon-carbon double bonds per 1,000 carbon atoms: 0.1 to 20 (2) The melt viscosity measured at 160°C using a rotational viscometer is 50 to 50,000 mPa·s (3) The softening point measured by the ring-ball method is 50-160°C

[0020] The polyolefin wax (X) is preferably at least one selected from the group consisting of (4), (5), and (6) below. (4) Contains polyolefin (A1) and silicon compound (B). (5)(A) is a silane-modified polyolefin (A2). (6)(A) is silane-crosslinked polyolefin (A3). Of the above (4) to (6), (5) and (6) are preferred, and (6) is even more preferred.

[0021] Examples of the silicon compound (B) mentioned above include silica (silicon dioxide). The average primary particle size of silica is preferably 5 to 100 nm, and more preferably 10 to 50 nm.

[0022] The polyolefin wax (X) has a silicon content (by weight) measured by fluorescent X-rays of 100 to 10,000 ppm, preferably 200 to 5,000 ppm, and more preferably 400 to 2,500 ppm. The silicon content of polyolefin wax (X) can be measured under the following conditions. • X-ray fluorescence analyzer "supermini200", manufactured by Rigaku Corporation Calibration curve method

[0023] The polyolefin wax (X) may consist solely of polyolefin (A), but based on the weight of (X), the weight of (A) is preferably 90% by weight or more, and more preferably 97% by weight or more. The polyolefin wax (X) may contain, in addition to the polyolefin (A) described above, known resin additives (for example, hindered phenol-based antioxidants).

[0024] Polyolefin wax (X) is applicable to a variety of uses and is particularly suitable as a modifier for thermoplastic resins and asphalt.

[0025] <Thermoplastic resin (E)> Examples of thermoplastic resins (E) in the present invention include polyolefin resins (E1) [polypropylene (PP), ethylene / propylene copolymer, polyethylene (PE), etc.]; polystyrene resins (E2) [polymers composed of vinyl group-containing aromatic hydrocarbons alone and one or more selected from the group consisting of vinyl group-containing aromatic hydrocarbons and butadiene; for example, polystyrene (PS) and high-impact polystyrene]; and mixtures of two or more of these. Note that (E1) and (A) can be distinguished by the number of carbon-carbon double bonds. Of the thermoplastic resins (E) mentioned above, (E1) and (E2) are preferred, (E1) is more preferred, and polypropylene is particularly preferred.

[0026] <Thermoplastic resin composition (Y)> The thermoplastic resin composition (Y) of the present invention contains the above-mentioned polyolefin wax (X) and thermoplastic resin (E). The weight ratio [(X) / (E)] of polyolefin wax (X) to thermoplastic resin (E) is preferably 1 / 99 to 20 / 80, and more preferably 5 / 95 to 15 / 85.

[0027] The thermoplastic resin composition (Y) can be obtained by melt-mixing a polyolefin wax (X), a thermoplastic resin (E), and optionally the known resin additive. At this time, a resin additive similar to the resin additive contained in the polyolefin wax (X) may be added to the resin composition (Y). Generally, a method of melt-mixing can be applied in which each component, in pellet or powder form, is mixed in a suitable mixer (such as a Henschel mixer), and then melt-mixed in an extruder to form pellets.

[0028] <Molded products> The molded article (Z) of the present invention is formed from a thermoplastic resin composition (Y). Examples of molding methods include injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, and film molding (casting method, tenter method, and inflation method, etc.). Depending on the purpose, the article can be molded using any method that incorporates means such as single-layer molding, multi-layer molding, or foam molding.

[0029] <Asphalt mixture (α)> The asphalt mixture (α) of the present invention comprises polyolefin wax (X), asphalt (K), and aggregate (L).

[0030] Examples of asphalt (K) in this invention include petroleum asphalt (straight asphalt, blown asphalt, semi-blown asphalt, cutback asphalt, etc.) and natural asphalt (lake asphalt, etc.). Examples of aggregate (L) in the present invention include crushed stone, pebbles, gravel, sand, and ceramics.

[0031] Asphalt mixture (α) is obtained by melting and mixing, for example, (X), (K), (L), and optionally known additives for asphalt mixtures, under heating (e.g., 160-200°C) using a known stirring device. Furthermore, based on the total weight of (X), (K), and (L), (X) is preferably 0.2 to 5% by weight, more preferably 0.5 to 2% by weight, (K) is preferably 2 to 10% by weight, more preferably 3 to 6% by weight, and (L) is preferably 85 to 97.8% by weight, more preferably 92 to 96.5% by weight.

[0032] <Pavement body (β)> The pavement body (β) of the present invention is made by paving with an asphalt mixture (α). The pavement body is used, for example, for road paving. The pavement body is obtained, for example, by applying an asphalt mixture (α) to a road or the like to form a pavement body (asphalt pavement layer). [Examples]

[0033] The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, parts represent parts by weight, and percentages other than mol% represent weight percentages.

[0034] <Example 1> 1000g of polyolefin (A0-1) [polyethylene, trade name "Novatec LD LJ902", manufactured by Nippon Polyethylene Co., Ltd.] was charged into a reaction vessel, and while supplying 60mL / min of nitrogen to the gas phase, it was heated and melted using a mantle heater, and thermal reduction was carried out at 380°C for 20 minutes while stirring to obtain polyolefin (A-1). Furthermore, polyolefin (A-1) had 1.5 carbon-carbon double bonds per 1,000 carbon atoms, a melt viscosity of 510 mPa·s at 160°C, and a softening point of 110°C. Next, 100 parts of (A-1) and 0.1 parts of silicon compound (B-1) [silicon dioxide, trade name "Roseal QS-09", manufactured by Tokuyama Corporation] were melt-kneaded to obtain polyolefin wax (X-1). The silicon content of polyolefin wax (X-1) was 850 ppm.

[0035] <Example 2> 1000g of polyolefin (A0-2) [silane-modified polypropylene, trade name "Linkron XPM-800H", manufactured by Mitsubishi Chemical Corporation] was charged into a reaction vessel. While supplying 60mL / min of nitrogen to the gas phase, it was heated and melted using a mantle heater, and thermal depolymerization was carried out at 400°C for 15 minutes with stirring to obtain polyolefin (A-2). The obtained polyolefin (A-2) was used as polyolefin wax (X-2). Furthermore, polyolefin (A-2) had 2.5 carbon-carbon double bonds per 1,000 carbon atoms, a melt viscosity of 1,000 mPa·s at 160°C, and a softening point of 112°C. The silicon content of polyolefin wax (X-2) was 3,000 ppm.

[0036] <Example 3> 1000g of polyolefin (A0-3) [silane-crosslinked polyethylene, used electrical wire insulation material, silicon content 1,800ppm] was charged into a reaction vessel, and while supplying 60mL / min of nitrogen to the gas phase, it was heated and melted using a mantle heater, and thermal reduction was carried out at 410°C for 15 minutes while stirring to obtain polyolefin (A-3). The obtained polyolefin (A-3) was used as polyolefin wax (X-3). Furthermore, the polyolefin (A-3) had 1.5 carbon-carbon double bonds per 1,000 carbon atoms, a melt viscosity of 500 mPa·s at 160°C, and a softening point of 110°C. The silicon content of the polyolefin wax (X-3) was 1,800 ppm.

[0037] <Example 4> 1000g of polyolefin (A0-4) [butadiene-isoprene-styrene copolymer (containing silica), resin pellets recovered from used automobile tires, silicon content 3,000 ppm] was charged into a reaction vessel. While supplying 60 mL / min of nitrogen to the gas phase, the mixture was heated and melted using a mantle heater, and thermal depolymerization was carried out at 380°C for 30 minutes with stirring to obtain polyolefin (A-4). The obtained polyolefin (A-4) was used as polyolefin wax (X-4). Furthermore, the polyolefin (A-4) had 0.2 carbon-carbon double bonds per 1,000 carbon atoms, a melt viscosity of 5,000 mPa·s at 160°C, and a softening point of 80°C. The silicon content of the polyolefin wax (X-4) was 3,000 ppm.

[0038] <Comparative Example 1> 1000g of polyolefin (A0-1) [polyethylene, trade name "Novatec LD LJ902", manufactured by Nippon Polyethylene Co., Ltd.] was charged into a reaction vessel, and while supplying 60mL / min of nitrogen to the gas phase, it was heated and melted using a mantle heater, and thermal reduction was carried out at 320°C for 20 minutes while stirring to obtain polyolefin (ratio A-1). The obtained polyolefin (ratio A-1) was used as is as polyolefin wax (ratio X-1). Furthermore, the polyolefin (ratio A-1) had 0.1 carbon-carbon double bonds per 1,000 carbon atoms, a melt viscosity of 970,000 mPa·s at 160°C, and a softening point of 120°C. Next, 100 parts of (Ratio A-1) and 0.1 parts of a silicon compound (B-1) [silicon dioxide, trade name "Roseal QS-09", manufactured by Tokuyama Corporation] were melt-kneaded to obtain polyolefin wax (Ratio X-1). The silicon content of the polyolefin wax (Ratio X-1) was 850 ppm.

[0039] <Examples 11-14, Comparative Examples 11-12> According to the formulations shown in Table 1, polyolefin wax (X) and thermoplastic resin (E) were blended in a Henschel mixer for 3 minutes, and then melt-kneaded in a vented twin-screw extruder at 260°C under conditions of a rotation speed of 90 rpm and a residence time of 2 minutes to obtain each thermoplastic resin composition (Y). Each of the obtained antistatic resin compositions (Y) was used to produce molded products (Z) (100 mm long, 100 mm wide, 2 mm thick) using an injection molding machine [product name "PS40E5ASE", Nissei Plastic Industrial Co., Ltd.] at a cylinder temperature of 260°C and a mold temperature of 80°C. Each of the obtained molded products (Z) was evaluated according to the <evaluation method> described below. The results are shown in Table 1.

[0040] <Evaluation Method>

[0041] (1) Adhesion (unit: N / mm) A molded product (Z) and aluminum foil (50 μm thick) were pressed at 200°C using a heated press to create test specimens. Then, the peel strength (under 90° conditions) was measured using an autograph in accordance with JIS Z0237:2009.

[0042] (2) Surface resistivity (unit: Ω / sq) The molded product (Z) was measured using a super-insulation meter "DSM-8103" [manufactured by Toa Denpa Kogyo Co., Ltd.] under conditions of 23°C and 50% RH humidity.

[0043] [Table 1]

[0044] <Examples 21-24, Comparative Examples 21-22> According to the composition (parts) shown in Table 2, aggregate (L) was placed in a mixer equipped with a heating device and heated to 175°C. Then, polyolefin wax (X) and asphalt (K) were added and mixed at 175°C for 10 minutes to obtain each asphalt mixture (α). Each obtained asphalt mixture (α) was evaluated according to the <Evaluation Method> described below. The results are shown in Table 2.

[0045] <Evaluation Method>

[0046] (3) Dynamic stability (unit: cycles / mm) For each asphalt mixture (α), dynamic stability was determined based on the wheel tracking test: 3-7-3 "Wheel Tracking Test Method" of the Japan Road Association's "Pavement Testing Method Handbook" (superimposed load: 690.7N, test temperature: 60℃, number of runs: 2520, running method: crank type).

[0047] (4) Residual stability (%) Each asphalt mixture (α) was evaluated based on the Pavement Survey and Testing Methods Handbook B001, "Marshall Stability Test Method." A test specimen with a diameter of approximately 10.2 cm and a height of approximately 6.3 cm was prepared using a Marshall compaction tester. This specimen was placed in a water tank set at 60°C for 30 minutes, then removed and placed horizontally in a Marshall stability test loading device (radius of curvature 5.08 cm). A load was applied at a speed of 50 mm / min, and the maximum load (standard stability) shown before the specimen fractured was determined. Furthermore, the maximum load (immersion stability) after 48 hours of immersion in the water tank was used, and the residual stability (%) was calculated using the following formula. Residual stability (%) = (water stability / standard stability) × 100

[0048] [Table 2]

[0049] Table 1 shows that the polyolefin wax (X) of the present invention provides thermoplastic resin composition (Y) with superior adhesion and superior antistatic properties compared to comparative materials. Furthermore, the results in Table 2 show that the polyolefin wax (X) of the present invention provides the asphalt mixture (α) with superior dynamic stability and superior residual stability compared to the comparative product. [Industrial applicability]

[0050] The polyolefin wax (X) of the present invention is applicable to a variety of uses and is particularly suitable as a modifier for thermoplastic resins and asphalt.

Claims

1. A polyolefin wax (X) containing a polyolefin (A) that satisfies the following conditions (1) to (3), wherein the silicon content measured by fluorescent X-rays is 100 to 10,000 ppm. (1) Number of carbon-carbon double bonds per 1,000 carbon atoms: 0.1 to 20 (2) The melt viscosity measured at 160°C using a rotational viscometer is 50 to 50,000 mPa·s (3) The softening point measured by the ring-ball method is 50 to 160°C

2. The polyolefin wax (X) according to claim 1, wherein the monomer constituting the polyolefin (A) is at least one selected from the group consisting of ethylene, propylene, butene, butadiene, and isoprene.

3. The polyolefin wax (X) according to claim 1, wherein the polyolefin wax (X) is at least one selected from the group consisting of (4), (5), and (6) below. (4) A compound containing a polyolefin (A1) and a silicon compound (B) (5) (A) is a silane-modified polyolefin (A2) (6) (A) is a silane-crosslinked polyolefin (A3)

4. A thermoplastic resin composition (Y) comprising the polyolefin wax (X) and thermoplastic resin (E) described in claim 1.

5. A molded article obtained by molding the thermoplastic resin composition (Y) described in claim 4.

6. An asphalt mixture (α) comprising the polyolefin wax (X) described in claim 1, asphalt (K), and aggregate (L).

7. A paved body (β) made by paving with the asphalt mixture (α) described in claim 6.

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