Acid-modified polyethylene wax, ink compositions, and paints

Abstract

To provide an acid-modified polyethylene wax with excellent abrasion resistance and slip resistance, an ink composition containing the acid-modified polyethylene wax, and a paint containing the acid-modified polyethylene wax. [Solution] Acid-modified polyethylene wax is a modified product in which an ethylene homopolymer is modified by an acid. The density of acid-modified polyethylene wax is 960 kg / m³. 3 More than 990kg / m 3 The following applies: The acid value of acid-modified polyethylene wax is between 10 mg KOH / g and 70 mg KOH / g.

Description

[Technical Field]

[0001] The present invention relates to acid-modified polyethylene wax, ink compositions, and paints, and more particularly to acid-modified polyethylene wax, ink compositions containing the acid-modified polyethylene wax, and paints containing the acid-modified polyethylene wax. [Background technology]

[0002] Traditionally, wax has been incorporated into ink compositions and paints from the standpoint of abrasion resistance.

[0003] As such a wax, polyolefin wax for coating materials, which is an ethylene copolymer, has been proposed (for example, manufacturing example 3 in Patent Document 1). The density of this polyolefin wax for coating materials is 977 kg / m³. 3 The acid value is 0 mgKOH / g. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2003-201436 [Overview of the project] [Problems that the invention aims to solve]

[0005] On the other hand, incorporating wax has the drawback of reducing slip resistance. In other words, there tends to be a trade-off between wear resistance and slip resistance.

[0006] The present invention provides an acid-modified polyethylene wax with excellent abrasion resistance and slip resistance, an ink composition containing the acid-modified polyethylene wax, and a paint containing the acid-modified polyethylene wax. [Means for solving the problem]

[0007] [[1]] The present invention provides an acid-modified polyethylene wax which is a modified product obtained by modifying an ethylene homopolymer with an acid, and has a density of 960 kg / m 3 or more and 990 kg / m 3 or less, and an acid value of 10 mgKOH / g or more and 70 mgKOH / g or less.

[0008] [[2]] The present invention includes the acid-modified polyethylene wax according to the above [1], which has a penetration of 4 dmm or less.

[0009] [[3]] The present invention includes the acid-modified polyethylene wax according to the above [1] or [2], which has a softening point of 110°C or higher and 150°C or lower.

[0010] [[4]] The present invention includes the acid-modified polyethylene wax according to any one of the above [1] to [3], which has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 1,000 or more and 10,000 or less.

[0011] [[5]] The present invention includes the acid-modified polyethylene wax according to any one of the above [1] to [4], which has an average particle diameter D 50 of 2 µm or more and 30 µm or less.

[0012] [[6]] The present invention includes an ink composition containing the acid-modified polyethylene wax according to any one of the above [1] to [5].

[0013] [[7]] The present invention includes a coating material containing the acid-modified polyethylene wax according to any one of the above [1] to [5].

Effects of the Invention

[0014] In the acid-modified polyethylene wax of the present invention, the density is 960 kg / m 3 or more and 990 kg / m 3 or less, and the acid value is 10 mgKOH / g or more and 70 mgKOH / g or less. Therefore, the acid-modified polyethylene wax is excellent in abrasion resistance and slip resistance.

[0015] The ink composition of the present invention comprises the acid-modified polyethylene wax of the present invention. Therefore, it is excellent in abrasion resistance and slip resistance.

[0016] The coating material of the present invention comprises the acid-modified polyethylene wax of the present invention. Therefore, it is excellent in abrasion resistance and slip resistance. MODE FOR CARRYING OUT THE INVENTION

[0017] 1. Acid-modified polyethylene wax The acid-modified polyethylene wax is a modified product obtained by modifying a homopolymer of ethylene with an acid. In other words, the acid-modified polyethylene wax is a graft-modified product of a homopolymer of ethylene with an acid.

[0018] <Ethylene Homopolymer> The ethylene homopolymer is obtained by polymerizing ethylene. Specifically, ethylene is polymerized in the presence of a catalyst.

[0019] Examples of the catalyst include titanium component-containing catalysts described in Japanese Patent Application Laid-Open No. H08-302083.

[0020] Specifically, the titanium component-containing catalyst is a reaction product of a reaction product of an alcohol adduct of a magnesium compound (preferably an ethanol adduct of magnesium chloride) and an aluminum compound (preferably diethylaluminum monochloride) with a titanium compound (e.g., titanium tetrachloride).

[0021] The catalyst is formulated such that, in terms of atoms, the titanium component is 0.001 mmol to 0.010 mmol, preferably 0.005 mmol to 0.009 mmol.

[0022] The supply amount of ethylene is such that, for example, the total pressure is 30 kg / cm 2 to 50 kg / cm 2 , preferably 35 kg / cm 2~45kg / cm 2 , more preferably 39 kg / cm³ 2 ~43kg / cm 2 Adjust it so that it works.

[0023] The polymerization conditions include a polymerization temperature of, for example, 100°C to 190°C, preferably 150°C to 180°C. The polymerization time is 10 minutes to 240 minutes, preferably 30 minutes to 60 minutes.

[0024] This process produces a homopolymer of ethylene.

[0025] The weight-average molecular weight of an ethylene homopolymer is, for example, 500 to 9000, preferably 1500 to 7000, more preferably 2000 to 4000, and even more preferably 2500 to 3000.

[0026] Note that the weight-average molecular weight (Mw) of ethylene homopolymers is the polystyrene-equivalent molecular weight obtained by gel permeation chromatography (GPC).

[0027] The density of an ethylene homopolymer is, for example, 960 kg / m³. 3 ~990 kg / m 3 Preferably, 965 kg / m 3 ~972 kg / m 3 , comfortably, 966 kg / m 3 ~969 kg / m 3 That is the case.

[0028] The density of ethylene homopolymers can be measured using a density gradient tube in accordance with JIS K 7122.

[0029] The softening point of ethylene homopolymers is, for example, 110°C to 150°C, preferably 115°C to 140°C, more preferably 116°C to 130°C, and even more preferably 117°C to 120°C.

[0030] The softening point of ethylene homopolymers can be measured in accordance with JIS K 2207.

[0031] <Acid-modified polyethylene wax> Acid-modified polyethylene wax is obtained by modifying an ethylene homopolymer with an acid.

[0032] Acids have an ethylenically unsaturated bonding group. Examples of acids include unsaturated carboxylic acids.

[0033] 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.

[0034] Furthermore, unsaturated carboxylic acids include the acid anhydrides of the unsaturated carboxylic acids mentioned above.

[0035] 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.

[0036] Acids can be used alone or in combination of two or more types.

[0037] Acid-modified polyethylene wax is obtained by reacting the above-mentioned ethylene homopolymer with an acid. In this reaction, the acid grafts onto the ethylene homopolymer.

[0038] Specifically, first, the ethylene homopolymer is melted at, for example, 100°C to 190°C, preferably 150°C to 180°C.

[0039] Next, the acid and radical polymerization initiator are added, and the mixture is heated and stirred.

[0040] The proportion of acid added is, for example, 1 to 15 parts by mass, preferably 5 to 8 parts by mass, per 100 parts by mass of ethylene homopolymer.

[0041] Examples of radical polymerization initiators include organic peroxides (e.g., di-tert-butyl peroxide).

[0042] The blending ratio of the radical polymerization initiator is, for example, 0.1 to 5.0 parts by mass, preferably 1.0 to 3 parts by mass, per 100 parts by mass of the ethylene homopolymer.

[0043] Radical polymerization initiators can be used alone or in combination of two or more types.

[0044] 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.

[0045] This process is used to produce acid-modified polyolefin wax.

[0046] Furthermore, if necessary, the acid-modified polyolefin wax can be pulverized afterward.

[0047] The grinding method is not particularly limited, but a jet mill is preferred. A jet mill reduces heat generation during grinding and offers excellent productivity.

[0048] In a jet mill, the grinding conditions are such that the discharge rate is, for example, 1 kg / hour to 10 kg / hour, and the grinding pressure is, for example, 0.1 MPa to 1.0 MPa.

[0049] This allows for the pulverization of acid-modified polyolefin wax.

[0050] The average particle size D50 of the acid-modified polyolefin wax before grinding is, for example, 100 μm to 300 μm, preferably 150 μm to 250 μm, and more preferably 200 μm to 220 μm.

[0051] Furthermore, the average particle size D50 of the acid-modified polyolefin wax after grinding is, for example, 2 μm to 30 μm, preferably 5 μm to 20 μm, more preferably 9 μm to 15 μm, and even more preferably 10 μm to 12 μm.

[0052] More specifically, the average particle size D50 of the acid-modified polyolefin wax after grinding is, from the viewpoint of abrasion resistance, for example, 2 μm or more, preferably 5 μm or more, more preferably 9 μm or more, and even more preferably 10 μm or more. Also, from the viewpoint of abrasion resistance, for example, 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 12 μm or less.

[0053] The average particle size can be measured using a known particle size analyzer as the 50% cumulative value (D50) in the volume fraction particle size distribution curve.

[0054] The weight-average molecular weight of the acid-modified polyethylene wax is, for example, 1000 to 10000, preferably 2000 to 7000, more preferably 2500 to 5000, and even more preferably 2800 to 3500.

[0055] More specifically, the weight-average molecular weight of the acid-modified polyethylene wax is, for example, 1000 or more, preferably 2000 or more, more preferably 2500 or more, and even more preferably 2800 or more, from the viewpoint of abrasion resistance. Also, for example, from the viewpoint of pulverability, it is 10000 or less, preferably 7000 or less, more preferably 5000 or less, and even more preferably 3500 or less.

[0056] The weight-average molecular weight (Mw) of acid-modified polyethylene wax is the polystyrene-equivalent molecular weight obtained by gel permeation chromatography (GPC).

[0057] The density of acid-modified polyethylene wax is 960 kg / m³. 3 ~990 kg / m 3 Preferably, 963 kg / m 3 ~980 kg / m 3 More preferably, 964 kg / m 3 ~970 kg / m 3 That is the case.

[0058] For more details, the density of acid-modified polyethylene wax is 960 kg / m³. 3 Preferably, 963 kg / m 3 More preferably, 964 kg / m 3 In addition, 990 kg / m 3 Preferably, 980 kg / m 3 More preferably, 970 kg / m 3 The following applies:

[0059] If the density of the acid-modified polyethylene wax is above the lower limit mentioned above, its pulverability and slip resistance can be improved.

[0060] On the other hand, if the density of the acid-modified polyethylene wax is below the lower limit mentioned above, its pulverability and slip resistance will decrease.

[0061] Furthermore, if the density of the acid-modified polyethylene wax is below the above upper limit, the abrasion resistance can be improved.

[0062] On the other hand, if the density of the acid-modified polyethylene wax exceeds the above upper limit, its abrasion resistance decreases.

[0063] The density of acid-modified polyethylene wax can be measured using a density gradient tube in accordance with JIS K 7122.

[0064] The acid value (JIS K5902) of acid-modified polyethylene wax is 10 mg KOH / g to 70 mg KOH / g, preferably 20 mg KOH / g to 65 mg KOH / g, more preferably 30 mg KOH / g to 60 mg KOH / g, even more preferably 40 mg KOH / g to 50 mg KOH / g, and most preferably 41 mg KOH / g to 45 mg KOH / g.

[0065] More specifically, the acid value of the acid-modified polyethylene wax is 10 mg KOH / g or more, preferably 20 mg KOH / g or more, more preferably 30 mg KOH / g or more, even more preferably 40 mg KOH / g or more, particularly preferably 41 mg KOH / g or more, and 70 mg KOH / g or less, preferably 65 mg KOH / g or less, more preferably 60 mg KOH / g or less, even more preferably 50 mg KOH / g or less, particularly preferably 45 mg KOH / g or less.

[0066] If the acid value of the acid-modified polyethylene wax is above the lower limit mentioned above, the abrasion resistance and slip resistance can be improved.

[0067] On the other hand, if the acid value of the acid-modified polyethylene wax is below the lower limit mentioned above, its abrasion resistance and slip resistance will decrease.

[0068] Furthermore, if the acid value of the acid-modified polyethylene wax is below the above upper limit, the pulverizability can be improved.

[0069] On the other hand, if the acid value of the acid-modified polyethylene wax exceeds the above upper limit, its pulverizability decreases.

[0070] The softening point of acid-modified polyethylene wax is, for example, 110°C to 150°C, preferably 112°C to 140°C, more preferably 113°C to 130°C, and even more preferably 115°C to 120°C.

[0071] More specifically, the softening point of the acid-modified polyethylene wax is, for example, 110°C or higher, preferably 112°C or higher, more preferably 113°C or higher, and even more preferably 115°C or higher, from the viewpoint of pulverability and slip resistance, and from the viewpoint of abrasion resistance, for example, 150°C or lower, preferably 140°C or lower, more preferably 130°C or lower, and even more preferably 120°C or lower.

[0072] The softening point of acid-modified polyethylene wax can be measured in accordance with JIS K 2207.

[0073] From the viewpoint of pulverability, the penetration of the acid-modified polyethylene wax is, for example, 4 dmm or less, preferably 2 dmm or less, and more preferably 0 dmm.

[0074] The method for measuring the penetration of acid-modified polyethylene wax will be described in detail in the examples below.

[0075] <Effects and Effects> In acid-modified polyethylene wax, the density is 960 kg / m³. 3 More than 990kg / m 3 The following conditions apply, and the acid value is between 10 mg KOH / g and 70 mg KOH / g. Therefore, it exhibits excellent wear resistance and slip resistance.

[0076] For more details, the density of the acid-modified polyethylene wax is 960 kg / m³. 3 If the above conditions are met, the slipperiness of the material itself will be reduced, thus improving its slip resistance.

[0077] Furthermore, the density of the acid-modified polyethylene wax is 990 kg / m³. 3 If the following conditions are met, the material will be crushed and spread out due to friction, allowing for uniform application. Therefore, wear resistance is improved.

[0078] Furthermore, if the acid value of the acid-modified polyethylene wax is 10 mg KOH / g or higher, the detachment of the acid-modified polyethylene wax from the resin (e.g., polar resin) during wear can be suppressed, thereby improving wear resistance and slip resistance.

[0079] Furthermore, if the acid value of the acid-modified polyethylene wax is 70 mg KOH / g or less, the decrease in crystallinity can be suppressed, and the pulverizability can be improved.

[0080] Furthermore, because acid-modified polyethylene wax can improve abrasion resistance and slip resistance, it can be suitably used as an additive in ink compositions and paints.

[0081] 2. Ink composition The ink composition comprises a pigment, a binder, an aqueous resin, and an acid-modified polyethylene wax.

[0082] The pigments are not particularly limited and include, for example, inorganic pigments and organic pigments. Examples of inorganic pigments include calcium carbonate, talc, and kaolin. Examples of organic pigments include phthalocyanine blue, phthalocyanine green, quinacridone red, and indanthrene orange.

[0083] Furthermore, commercially available pigments can also be used. An example of a commercially available product is the WS series (manufactured by Toyo Ink Co., Ltd.).

[0084] The pigment can also be prepared as a dispersion in water or a solvent. The solid content concentration of the pigment dispersion is, for example, 10% to 40% by mass.

[0085] The pigment content is, for example, 1% to 20% by mass relative to the ink composition.

[0086] Pigments can be used individually or in combination of two or more types.

[0087] A binder adheres the pigments to the surface. Examples of binders include water-based emulsions (e.g., acrylic emulsions). Binders can be used alone or in combination of two or more types.

[0088] The binder can also be prepared as a varnish. The solid content concentration of the binder varnish is, for example, 20% to 50% by mass.

[0089] The binder content is, for example, 5% to 40% by mass relative to the ink composition.

[0090] Examples of water-based resins include water-soluble acrylic resins.

[0091] The content of the water-based resin is, for example, 3% to 30% by mass relative to the ink composition.

[0092] The content of acid-modified polyethylene wax is, for example, 0.1% to 5% by mass, preferably 0.3% to 1.2% by mass, and more preferably 0.7% to 1.1% by mass, relative to the ink composition.

[0093] The ink composition may contain additives in appropriate proportions as needed. Examples of additives include surfactants, coating modifiers, leveling agents, defoamers, antioxidants, UV absorbers, and plasticizers. Additives may be used individually or in combination of two or more types.

[0094] Furthermore, the ink composition preferably does not contain anti-slip agents (e.g., silica sand, glass beads). Specifically, because this ink composition contains the above-mentioned acid-modified polyethylene wax, it can improve abrasion resistance and has excellent slip resistance, so even if the ink composition does not contain anti-slip agents, it will have excellent slip resistance.

[0095] The ink composition is obtained by mixing a pigment, a binder, an aqueous resin, an acid-modified polyethylene wax, and additives as needed. The ink composition can also be diluted as needed.

[0096] The ink composition contains acid-modified polyethylene wax. Therefore, it has excellent abrasion resistance and slip resistance.

[0097] 3.Paint The paint contains acid-modified polyethylene wax, resulting in excellent abrasion resistance and slip resistance.

[0098] Examples of such paints include architectural paints and automotive paints. [Examples]

[0099] 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.

[0100] <Synthesis of titanium-containing catalysts> Synthesis Example 1 In a glass autoclave (capacity 1.5 liters), 25 g of anhydrous magnesium chloride was suspended in 500 ml of hexane. Then, while maintaining the temperature at 30°C and stirring, 92 ml of ethanol was added dropwise over 1 hour, and the reaction was continued for another 1 hour. After the reaction was complete, 93 ml of diethylaluminum monolith was added dropwise over 1 hour, and the reaction was continued for another 1 hour. After the reaction was complete, 90 ml of titanium tetrachloride was added dropwise, and the temperature was raised to 80°C and the reaction was continued for 1 hour. After the reaction was complete, the solid of the suspension was washed by decantation with hexane. Washing was repeated until no free titanium was detected. This synthesized a titanium-containing catalyst.

[0101] Example 1 (Production of ethylene homopolymers) A 2-liter capacity stainless steel autoclave, purged with nitrogen, is filled with 930 ml of hexane and hydrogen at a rate of 20.0 kg / cm³. 2 The mixture was introduced until it reached (gauge pressure). Next, after raising the temperature to 170°C, polymerization was started by injecting 0.1 mmol of triethylaluminum, 0.4 mmol of ethylaluminum sesquichloride, and the titanium-containing catalyst from Synthesis Example 1 (0.008 mmol in atomic terms) under pressure with ethylene. Subsequently, the total pressure was increased to 40 kg / cm² by continuously supplying ethylene. 2 Polymerization was carried out at 170°C for 40 minutes while maintaining a gauge pressure. Polymerization was then stopped by adding a small amount of ethanol. Unreacted ethylene was then purged. This yielded a solution of ethylene homopolymer, which was then dried overnight under reduced pressure at 100°C. This resulted in obtaining the ethylene homopolymer.

[0102] (Manufacturing of acid-modified polyethylene wax) 800 g of the above-mentioned ethylene homopolymer was charged into a glass reactor and melted at 160°C under a nitrogen atmosphere. Next, 52.6 g of maleic anhydride and 11.1 g of di-t-butyl peroxide were continuously supplied at 160°C for 3 hours. After heating and reacting for 1 hour, the molten mixture was degassed in a 10 mmHg vacuum for 0.5 hours to remove volatile components, and then cooled. This yielded acid-modified polyethylene wax. Subsequently, the acid-modified polyethylene wax was pulverized using a jet mill.

[0103] (Manufacturing of ink compositions) A pigment dispersion (WS RED R-1, solid content concentration 18% by mass, manufactured by Toyo Ink Co., Ltd.), a water-based resin varnish (Joncryl 62J, water-soluble acrylic resin, solid content concentration 34% by mass, manufactured by BASF), a binder (Joncryl PDX7687, acrylic emulsion, solid content 42% by mass, manufactured by BASF), and distilled water were mixed. The mixing ratio was pigment dispersion / water-based resin varnish / binder / distilled water = 36.4 / 18.2 / 36.4 / 9. Subsequently, acid-modified polyethylene wax and a surfactant (Leodol TW-L120) were added. The mixing ratio was acid-modified polyethylene wax / surfactant = 5 / 6.5, and the content of acid-modified polyethylene wax in the ink composition was adjusted to 0.5% by mass or 1% by mass. This obtained the ink composition.

[0104] Example 2 Acid-modified polyethylene wax and ink compositions were obtained based on the same procedure as in Example 1. However, the formulations were modified based on the information in Table 1.

[0105] Comparative Example 1 An ink composition was obtained based on the same procedure as in Example 1. However, in Comparative Example 1, acid-modified polyethylene wax was not included.

[0106] Comparative Example 2 An ink composition was obtained based on the same procedure as in Example 1. However, in Comparative Example 2, as the acid-modified polyethylene wax, High Wax 1105A (maleic anhydride-modified ethylene-propylene copolymer, density 940 kg / m³) was used. 3 A material with a softening point of 108°C, a weight-average molecular weight of 4400, a penetration depth of 6dmm, an acid value of 60mgKOH / g, an average particle size D50 of 193μm, and the trade name "High Wax 1105A" was prepared and ground using a jet mill.

[0107] Comparative Example 3 An ink composition was obtained based on the same procedure as in Example 1. However, in Comparative Example 3, as the acid-modified polyethylene wax, High Wax 1105A (maleic anhydride-modified ethylene-propylene copolymer, density 940 kg / m³) was used. 3 A wax with a softening point of 108°C, weight-average molecular weight of 4400, penetration of 6dmm, acid value of 60mgKOH / g, average particle size D50 of 193μm, trade name "High Wax 1105A", manufactured by Mitsui Chemicals, Inc. was prepared and ground in a hammer mill. The grinding conditions in the hammer mill were a processing rate of 6.8kg / hour and a rotation speed of 3200rpm.

[0108] Comparative Example 4 An ink composition was obtained based on the same procedure as in Example 1. However, in Comparative Example 4, High Wax 200P (ethylene polymer, density 970 kg / m³) was used as the polyethylene wax. 3 A material with a softening point of 130°C, a weight-average molecular weight of 6700, a penetration of 0 dmm, an average particle size D50 of 139 μm, and the product name "High Wax 200P" (manufactured by Mitsui Chemicals, Inc.) was prepared and ground using a jet mill.

[0109] Comparative Example 5 An ink composition was obtained based on the same procedure as in Example 1. However, in Comparative Example 5, instead of acid-modified polyethylene wax, Celidust 8020TP (a copolymer of long-chain α-olefin and maleic anhydride, density 970 kg / m3, softening point 80°C, weight-average molecular weight 8800, penetration 5 d mm, acid value 90 mg KOH / g, average particle size D50 8.2 μm, trade name "Celidust 8020TP", manufactured by Clariant) was prepared. Also, grinding with a jet mill was not performed.

[0110] <Rating> [Weight average molecular weight (Mw)] The weight-average molecular weight (Mw) was measured for the ethylene homopolymers and acid-modified polyethylene waxes used in each example, as well as the acid-modified polyethylene wax used in each comparative example. Specifically, GPC measurements were performed under the following conditions. The weight-average molecular weight (Mw) was determined using a calibration curve created with commercially available monodisperse standard polystyrene, based on the measurement method described below. Density was also measured. The results are shown in Table 1. {conditions} Equipment: Gel permeation chromatograph HLC-8321GPC / HT model (manufactured by Tosoh Corporation) Solvent: o-dichlorobenzene Columns: TSKgelGMH6-HT x 2, TSKgelGMH6-HTL column x 2 (both manufactured by Tosoh Corporation) Flow rate: 1.0ml / min Sample: 0.1 mg / mL of dichlorobenzene solution Column temperature: 140℃ Injection volume: 400μl Detector: Differential refractometer Sampling time interval: 0.5 seconds

[0111] [density] The densities of the ethylene homopolymers and acid-modified polyethylene waxes used in each example, as well as the acid-modified polyethylene waxes used in each comparative example, were measured using a density gradient tube in accordance with JIS K7112. The results are shown in Table 1.

[0112] [Acid value] The acid value of the acid-modified polyethylene waxes in each example and comparative example was measured in accordance with JIS K5902. The results are shown in Table 1.

[0113] [Softening point] The softening points of the ethylene homopolymers and acid-modified polyethylene waxes used in each example, as well as the acid-modified polyethylene waxes used in each comparative example, were measured in accordance with JIS K2207. The results are shown in Table 1.

[0114] [Penetration] The penetration depth of the acid-modified polyethylene waxes in each example and comparative example was measured according to ASTM D1321. The measurement conditions were a temperature of 25°C, a load of 100g, and a penetration time of 5 seconds. The results are shown in Table 1.

[0115] [Average particle diameter D50] For each example and comparative example of acid-modified polyethylene wax, the average particle size D50 before and after grinding was measured wet using an LMS-3000 (laser diffraction / scattering particle size distribution analyzer). The results are shown in Table 1.

[0116] [Abrasion resistance] (Manufacturing of test specimens) The ink compositions of each example and comparative example (ink compositions with an acid-modified polyethylene wax content of 0.5% by mass, and ink compositions with an acid-modified polyethylene wax content of 1% by mass) were coated onto white cardboard (310 g / m² basis weight) using a bar coater No. 4. 2 The coating was applied to the sample. Afterward, it was treated in an oven at 60°C for 1 minute, and then dried in a constant temperature and humidity chamber at 23°C and 55% Rh for 24 hours. This produced test specimens with a coating film (thickness 3-4 μm).

[0117] (Abrasion test) A Sutherland abrasion test was performed on the test specimens. The measurement conditions were a load of 1816g (4lb), 120 friction cycles, and K-liner friction paper (220g / m² basis weight). 2The test was conducted using [specific method / tool]. Abrasion resistance was evaluated based on the following criteria. The results are shown in Table 1. {standard} A: Less than 20% of the areas that were rubbed showed peeling. B: In the areas that were rubbed, peeling occurred in 20% to less than 60% of the area. C: More than 60% of the friction-affected areas showed peeling.

[0118] [Slip resistance] (Manufacturing of test specimens) The ink compositions of each example and comparative example (ink compositions containing 1% by mass of acid-modified polyethylene wax) were coated using a bar coater No. 4 with K Liner (220 g / m² basis weight). 2 The coating was applied to the sample. Afterward, it was treated in an oven at 60°C for 1 minute, and then dried in a constant temperature and humidity chamber at 23°C and 55% Rh for 24 hours. This produced test specimens with a coating film (thickness 3-4 μm).

[0119] (Slip resistance test) The slip angle was measured on the test specimen using a static friction coefficient measuring device. Specifically, the coating surface of the test specimen was coated with K-liner (220 g / m²). 2 The test specimen was placed on a surface, a 200g load was applied, and the angle at which it began to slide (slip angle) was measured when it was tilted at a speed of 10° / 6 seconds. The results are shown in Table 1. It can be seen that the larger the slip angle, the better the slip resistance.

[0120] [Table 1]

Claims

1. A modified ethylene homopolymer is a modified product obtained by being altered by an acid. The density is 960 kg / m³. ３ More than 990kg / m ３ The following: Acid-modified polyethylene wax having an acid value of 10 mg KOH / g or more and 70 mg KOH / g or less.

2. The acid-modified polyethylene wax according to claim 1, wherein the penetration depth is 4 d mm or less.

3. The acid-modified polyethylene wax according to claim 1, wherein the softening point is 110°C or higher and 150°C or lower.

4. The acid-modified polyethylene wax according to claim 1, wherein the weight-average molecular weight in polystyrene terms, as measured by gel permeation chromatography (GPC), is 1,000 or more and 10,000 or less.

5. Average particle diameter D ５０ The acid-modified polyethylene wax according to claim 1, wherein the particle size is 2 μm or more and 30 μm or less.

6. An ink composition comprising the acid-modified polyethylene wax described in any one of claims 1 to 5.

7. A paint comprising the acid-modified polyethylene wax described in any one of claims 1 to 5.

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