Surface modifier composition for thermoplastic resins, and thermoplastic resin composition containing the same.

Abstract

The present invention provides a surface modifier composition for thermoplastic resins that can improve the slipperiness and water resistance of thermoplastic resins, and a thermoplastic resin composition containing the same. [Solution] A surface modifier composition for thermoplastic resins comprising a secondary alcohol A having 23 to 61 carbon atoms and a dialkylketone B having 23 to 61 carbon atoms, wherein the mass ratio of the secondary alcohol A to the dialkylketone B (secondary alcohol A:dialkylketone B) is 70:30 to 99.9:0.1.

Description

Technical Field

[0001] The present invention relates to a surface modifier composition for thermoplastic resins and a thermoplastic resin composition containing the surface modifier composition.

Background Art

[0002] Since thermoplastic resins are easy to mold, they are used in a wide range of fields such as electronic devices, automobiles, printing, medical, furniture, household appliances, and food. In general, functions necessary for thermoplastic resins are imparted according to the required characteristics for each application. For example, various functions can be imparted to thermoplastic resins by surface treatment of molded products or addition of modifiers to thermoplastic resins. Among them, from the perspective of the usability of molded products of thermoplastic resins, a slip agent may be added to thermoplastic resins in order to improve the slipperiness of the surface of the molded products. For example, Patent Document 1 discloses a branched saturated primary fatty acid amide mixture having a specific structure as a slip agent for reducing the friction coefficient of thermoplastic resins.

[0003] On the other hand, in recent years, molded products of thermoplastic resins have been increasingly exposed to treatments such as washing away and wiping with water from the hygienic perspective such as virus countermeasures. Therefore, in molded products of thermoplastic resins, it is required to improve water resistance, that is, to maintain functions such as the appearance and slipperiness of the surface of the molded product even after being exposed to treatments such as washing away and wiping with water. For example, Patent Document 2 discloses a resin aqueous dispersion that can form a resin film having good water resistance. The resin aqueous dispersion is obtained by emulsion polymerization of a polymerizable compound in the presence of a reactive surfactant in which two or more hydrogen atoms of a phenyl group of polyoxyalkylene phenyl ether are each substituted with an arylalkyl group such as a benzyl group or a specific polymerizable unsaturated group. Patent Document 2 describes that the water whitening resistance of a resin film obtained from the resin aqueous dispersion is improved by using the above reactive surfactant.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-6122 [Patent Document 2] Japanese Patent Publication No. 2018-171592 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, when using the slip agent described in Patent Document 1, while it is possible to improve the slipperiness of the thermoplastic resin, it is not possible to suppress the change in surface gloss when the surface of the thermoplastic resin is washed or wiped with water. On the other hand, when using the reactive surfactant described in Patent Document 2, while it is possible to improve the water-resistance to whitening of the resin film, it is not possible to improve its slipperiness.

[0006] The present invention has been made in view of the above problems, and aims to provide a surface modifier composition for thermoplastic resins that can improve the slipperiness and water resistance of the surface of the thermoplastic resin. Furthermore, the present invention aims to provide a thermoplastic resin composition with improved surface slipperiness and water resistance. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the inventors of the present invention have found that a thermoplastic resin containing a composition in which a specific secondary alcohol and a dialkyl ketone are present in a specific ratio exhibits good surface slipperiness and excellent water resistance, thus completing the present invention.

[0008] In other words, the present invention provides the following surface modifier composition for thermoplastic resins. [1] A surface modifier composition for thermoplastic resins comprising a secondary alcohol A having 23 to 61 carbon atoms and a dialkylketone B having 23 to 61 carbon atoms, wherein the mass ratio of the secondary alcohol A to the dialkylketone B (secondary alcohol A:dialkylketone B) is 70:30 to 99.9:0.1.

[0009] Furthermore, the present invention provides the following thermoplastic resin compositions. [2] A thermoplastic resin composition comprising the surface modifier composition for thermoplastic resins described in [1] and a thermoplastic resin. [Effects of the Invention]

[0010] The surface modifier composition for thermoplastic resins of the present invention can improve the slipperiness and water resistance of the surface of thermoplastic resins. Furthermore, according to the present invention, it is possible to provide a thermoplastic resin composition with improved surface slipperiness and water resistance. [Modes for carrying out the invention]

[0011] The embodiments of the present invention will be described below, but the present invention is not limited to the embodiments described herein and can be modified in various ways without departing from the spirit of the invention. Furthermore, in this invention, a numerical range defined using the symbol "~" includes the numerical values ​​at both ends (upper and lower limits) of "~". For example, "2~10" represents the range of 2 to 10. Furthermore, within the numerical range described in the present invention, the upper or lower limit of that numerical range can be replaced with the values ​​shown in the examples or values ​​uniquely derived from the examples. Furthermore, among the numerical values ​​described to explain the present invention, the numerical values ​​that may include decimal places are, unless otherwise specified, obtained by rounding a digit that was one place smaller than the smallest digit included in the numerical value.

[0012] The surface modifier composition for thermoplastic resins of the present invention (sometimes simply referred to as "the surface modifier composition of the present invention" or "surface modifier composition") comprises a secondary alcohol A having 23 to 61 carbon atoms and a dialkylketone B having 23 to 61 carbon atoms, characterized in that the mass ratio of the secondary alcohol A to the dialkylketone B (secondary alcohol A:dialkylketone B) is 70:30 to 99.9:0.1. Furthermore, secondary alcohols and dialkylketones generally exhibit molecular weight distributions when analyzed by gel permeation chromatography (GPC). Therefore, in this invention, "number of carbon atoms" refers to the distribution of carbon atoms as analyzed by gel permeation chromatography (GPC). Note that "number of carbon atoms" refers to the number of carbon atoms in one molecule. Also, a carbon number of 23 to 61 means that the distribution of carbon atoms falls within the range of 23 to 61, and does not necessarily mean that the distribution of carbon atoms extends from 23 to 61.

[0013] Because the surface modifier composition of the present invention has low compatibility with thermoplastic resins alone, in thermoplastic resins into which the surface modifier composition of the present invention is blended, the surface modifier composition of the present invention becomes unevenly distributed on the surface, reducing the coefficient of friction of the surface. Furthermore, by containing the above-mentioned specific secondary alcohol A and dialkylketone B in the above-mentioned specific mass ratio, the crystallinity of secondary alcohol A is moderately reduced by dialkylketone B, and as a result, the crystallization rate and molecular orientation of the surface modifier composition are easily controlled. Therefore, on the surface of a thermoplastic resin where the surface modifier composition of the present invention is unevenly distributed, local crystallization of the surface modifier composition of the present invention is suppressed, and the above-mentioned secondary alcohol A and dialkylketone B are regularly oriented. As a result, the surface modifier composition of the present invention can further improve the slipperiness of the surface of the thermoplastic resin and can also impart gloss to the surface of the thermoplastic resin. Thermoplastic resins may change in surface gloss due to water washing, wiping with water, water adhesion, wiping off the adhered water, etc. (hereinafter referred to as "water washing treatment, etc."). However, when the surface modifier composition of the present invention is contained, the surface gloss is less likely to change even after water washing treatment, etc. In the present invention, "water resistance" may mean that the gloss change due to water on the surface of the thermoplastic resin is small. The surface of the thermoplastic resin may be the surface of a thermoplastic resin in a solid state, and may be the surface of a molded product formed into a desired shape, or the surface of a solid that has not undergone any molding process. In the surface modifier composition of the present invention, the crystallinity or molecular orientation of the surface modifier composition can be further controlled by adjusting the chain length of the organic group of secondary alcohol A or the alkyl group of dialkylketone B. This allows the effects of the present invention to be exhibited more significantly. In this specification, "the effects of the present invention to be exhibited more significantly" means that either or both of the following effects of the surface modifier composition of the present invention—the effect of improving the slipperiness of thermoplastic resins and the effect of the surface modifier composition of the present invention—are superior. The following describes each component contained in the surface modifier composition of the present invention.

[0014] [Secondary Alcohol A] The surface modifier composition of the present invention contains a secondary alcohol A having 23 to 61 carbon atoms. This secondary alcohol A is a compound that contains one hydroxyl group, and organic groups are bonded to both sides of the carbon atom to which the hydroxyl group is attached. That is, of the remaining three bonds of the carbon atom to which the hydroxyl group is attached, two are bonded to organic groups and one is bonded to a hydrogen atom. Furthermore, the number of carbon atoms in one molecule of this secondary alcohol A is 23 to 61. The secondary alcohol A contained in the surface modifier composition of the present invention may consist of a single compound, or, as described above, may be a mixture having a certain molecular weight distribution, that is, a mixture of two or more compounds. From the viewpoint of more significantly exerting the effects of the present invention, the surface modifier composition of the present invention preferably contains at least a secondary alcohol A having 27 to 57 carbon atoms as the secondary alcohol A, and more preferably contains at least a secondary alcohol A having 31 to 43 carbon atoms. Further, when the total mass of the secondary alcohol A is 100% by mass, the content of such a preferable secondary alcohol A is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.

[0015] The carbon number of the secondary alcohol A may be 23 to 61, but from the viewpoint of more significantly exerting the effects of the present invention, it is preferably 27 to 57, and more preferably 31 to 43.

[0016] From the viewpoint of more significantly exerting the effects of the present invention, among the alcohols contained in the surface modifier composition of the present invention, the content of the secondary alcohol A is preferably 99% by mass or more, and more preferably 99.9% by mass or more.

[0017] From the viewpoint of more significantly exerting the effects of the present invention, the two organic groups of the secondary alcohol A are preferably hydrocarbon groups, more preferably saturated or unsaturated aliphatic groups, and still more preferably alkyl groups.

[0018] The two organic groups of the secondary alcohol A may be the same or different. On the other hand, from the viewpoint of more significantly exerting the effects of the present invention, the difference in the carbon number of the two organic groups of the secondary alcohol A is preferably 2 or less, and more preferably 0.

[0019] The organic group of the secondary alcohol A may be linear, branched, or cyclic, but from the viewpoint of more significantly exerting the effects of the present invention, it is preferably linear.

[0020] Specific examples of the secondary alcohol A include 12-tricosanol, 14-heptacosanol, 16-hentriacontanol, 17-tritriacontanol, 18-pentatriacontanol, 19-heptatriacontanol, 20-nonatriacontanol, 21-hentetracontanol, 22-tritetracontanol, 24-heptatetracontanol, 26-henpentacontanol, 28-pentapentacontanol, and the like. Among them, from the viewpoint that the effects of the present invention are more significantly exerted, at least one selected from the group consisting of 16-hentriacontanol, 17-tritriacontanol, 18-pentatriacontanol, 19-heptatriacontanol, 20-nonatriacontanol, 21-hentetracontanol, and 22-tritetracontanol is preferably used.

[0021] The method for preparing the secondary alcohol A is not particularly limited. For example, in the presence of a metal oxide catalyst, a carboxylic acid having a desired organic group is reacted at a high temperature (preferably a temperature of 300 to 350 ° C) and a high pressure (preferably 0.1 to 5 MPa), and decarboxylated to obtain a ketone, and the obtained ketone is reduced to obtain the secondary alcohol A.

[0022] Examples of the usable metal oxide catalyst include magnesium oxide, calcium oxide, zinc oxide, and the like. The carboxylic acid having a desired organic group is not particularly limited, and examples thereof include lauric acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, eicosanoic acid, arachidic acid, behenic acid, lignoceric acid, hexacosanoic acid, and montanic acid.

[0023] On the other hand, ketones may be obtained using metal carboxylate salts such as magnesium carboxylate salts, calcium carboxylate salts, or zinc carboxylate salts instead of the above-mentioned carboxylic acid and metal oxide catalysts. Typical examples of metal carboxylate salts include magnesium stearate, calcium stearate, zinc stearate, magnesium behenate, calcium behenate, zinc behenate, magnesium palmitate, magnesium montanate, magnesium eicosanate, magnesium hexacosanate, and magnesium heptadecanoate.

[0024] The reduction method for reducing ketones is not particularly limited, and known methods such as catalytic reduction, in which hydrogen is reacted in the presence of a hydrogenation catalyst; hydride reduction using sodium borohydride, etc.; Lucher reduction; silane reduction; Meerwein-Pondorf-Varley reduction; or Wolff-Kishner reduction can be used.

[0025] [Dialkylketone B] The surface modifier composition of the present invention contains a dialkylketone B having 23 to 61 carbon atoms. The dialkylketone B is a compound containing one carbonyl group, with alkyl groups bonded to both sides of the carbon atom in the carbonyl group, and having 23 to 61 carbon atoms in one molecule. The dialkylketone B contained in the surface modifier composition of the present invention may consist of a single compound, or, as described above, may be a mixture having a certain molecular weight distribution, that is, a mixture of two or more compounds. To more clearly demonstrate the effects of the present invention, the surface modifier composition of the present invention preferably contains at least a dialkylketone B having 27 to 57 carbon atoms, and more preferably contains at least a dialkylketone B having 31 to 43 carbon atoms. Furthermore, when the total mass of dialkylketone B is 100% by mass, the content of such preferred dialkylketone B is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0026] The number of carbon atoms in the above-mentioned dialkylketone B may be 23 to 61, but is preferably 27 to 57, and more preferably 31 to 43, in order to more clearly exhibit the effects of the present invention.

[0027] In order to more clearly demonstrate the effects of the present invention, it is preferable that the content of the above-mentioned dialkylketone B among the ketones contained in the surface modifier composition of the present invention be 99% by mass or more, and more preferably 99.9% by mass or more.

[0028] The two alkyl groups of the above-mentioned dialkylketone B may be the same or different. On the other hand, in order to more clearly demonstrate the effects of the present invention, the difference in the number of carbon atoms between the two alkyl groups of the above-mentioned dialkylketone B is preferably 2 or less, and more preferably 0.

[0029] The alkyl group of the above-mentioned dialkylketone B may be linear, branched, or cyclic, but it is preferable that it be linear in order to more clearly exhibit the effects of the present invention.

[0030] Specific examples of the above-mentioned dialkylketone B include didodecylketone, ditridecylketone, ditetradecylketone, dipentadecylketone, dihexadecylketone, diheptadecylketone, heptadecylpentadecylketone, dioctadecylketone, dinonadecylketone, dieicosylketone, diheneicosylketone, didcosylketone, ditricosylketone, ditetracosylketone, dihexacosylketone, diheptacosylketone, and dioctacosylketone. Among these, at least one selected from the group consisting of dihexadecylketone, diheptadecylketone, dioctadecylketone, dinonadecylketone, dieicosylketone, and diheneicosylketone is preferably used in order to more clearly demonstrate the effects of the present invention.

[0031] The method for preparing the above-mentioned dialkylketone B is not particularly limited. For example, it can be prepared in the same manner as the method used to obtain the ketone as an intermediate in the preparation of the secondary alcohol A described above. That is, the above-mentioned dialkylketone B can be obtained by reacting a saturated fatty acid having a desired number of carbon atoms with a metal oxide catalyst at high temperature and high pressure, and then decarboxylating it. Alternatively, the above-mentioned dialkylketone B can be obtained by using a saturated fatty acid metal salt instead of the saturated fatty acid and metal oxide catalyst.

[0032] [Surface modifier composition] The surface modifier composition of the present invention contains the above-mentioned secondary alcohol A and the above-mentioned dialkylketone B in a mass ratio (secondary alcohol A:dialkylketone B) of 70:30 to 99.9:0.1. The above mass ratio (which may be denoted as "A:B" in the present invention) may be 70:30 to 99.9:0.1, but from the viewpoint of exhibiting the effects of the present invention more significantly, it is preferably 80:20 to 99.9:0.1, more preferably 90:10 to 99.5:0.5, and even more preferably 93:7 to 99:1.

[0033] When the total mass of the surface modifier composition of the present invention is 100 parts by mass, the total content of the secondary alcohol A and the dialkylketone B is not particularly limited, but is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, even more preferably 99 parts by mass or more, and may be 100 parts by mass, from the viewpoint that the effects of the present invention are easily exhibited.

[0034] Among the compounds constituting the secondary alcohol A, the carbon number of the compound with the highest content is defined as the carbon number a of the secondary alcohol A, and among the compounds constituting the dialkyl ketone B, the carbon number of the compound with the highest content is defined as the carbon number b of the dialkyl ketone B. When the absolute value of the difference between said a and b (|a - b|) makes, although it is not particularly limited preferably it is 0 to 20 or less, more preferably 0 to 10 or less, still more preferably 0 to 2 or less. When the difference between the carbon number a and the carbon number b is within the above-described range, the crystallinity of the secondary alcohol A is easily controlled appropriately by the dialkyl ketone B, so that the effects of the present invention are more significantly exhibited. Further, from the point that the effects of the present invention are more significantly exhibited, it is preferable that the carbon number a is larger than the carbon number b. When the secondary alcohol A is composed of a single compound, the carbon number a is the carbon number of the single compound constituting the secondary alcohol A. When the dialkyl ketone B is composed of a single compound, the carbon number b is the carbon number of the single compound constituting the dialkyl ketone B. The compound with the highest content in the mixture can be specified by GC measurement under the following conditions. <GC measurement conditions> Apparatus: SHIMAZU GC-2030 Column: Agilent DB-1HT 15m × 0.25mm × 0.10μm Carrier gas: Nitrogen Gas flow rate: 134.4 mL / min (split, 50) Inlet temperature: 400°C Detector (temperature): FID (400°C) Column temperature (heating rate): 100°C - 390°C (10°C / min) Measurement sample: Toluene solution (10 mg / g) Analysis: Area %

[0035] 〔Method for producing surface modifier composition〕 The method for producing the surface modifier composition of the present invention is not particularly limited. For example, the surface modifier composition of the present invention can be obtained by individually synthesizing the secondary alcohol A and dialkylketone B described above, and then mixing them. When mixing individually synthesized components, it is preferable to heat and dissolve them at a temperature above the melting point of each component to ensure uniform mixing. Furthermore, it is preferable to then cool and solidify the heated and dissolved mixture, and then perform a micronization treatment such as pulverization or granulation to produce the surface modifier composition of the present invention. This makes it possible to suppress variations in the quality of the resulting surface modifier composition. Alternatively, after obtaining dialkylketone B, a portion of it may be reduced to obtain secondary alcohol A, thereby synthesizing secondary alcohol A and dialkylketone B together.

[0036] [Thermoplastic resin composition] The thermoplastic resin composition of the present invention contains the surface modifier composition of the present invention described above and a thermoplastic resin. The thermoplastic resin composition of the present invention has improved surface slipperiness and water resistance due to the inclusion of the surface modifier composition of the present invention. In the description of the surface modifier composition of the present invention, the term "thermoplastic resin" has sometimes been used to mean a thermoplastic resin into which the surface modifier composition of the present invention is blended. However, in the thermoplastic resin composition of the present invention, "thermoplastic resin" means a thermoplastic resin alone that does not contain the surface modifier composition of the present invention.

[0037] In the thermoplastic resin composition of the present invention, the content of the surface modifier composition of the present invention may be in the range of 0.01 to 10 parts by mass per 100 parts by mass of thermoplastic resin. When the content of the surface modifier composition of the present invention is above the lower limit, the effect of the surface modifier composition of the present invention is easily exhibited, and when it is below the upper limit, the physical properties of the thermoplastic resin are easily maintained. From this viewpoint, the content of the surface modifier composition of the present invention per 100 parts by mass of thermoplastic resin may be in the range of 1 to 10 parts by mass, or in the range of 3 to 7 parts by mass. The surface modifier composition of the present invention contained in the thermoplastic resin composition may be a single type or a combination of two or more types.

[0038] The thermoplastic resin contained in the thermoplastic resin composition of the present invention is not particularly limited and may be amorphous or crystalline, or a thermoplastic elastomer, and can be appropriately selected depending on the application. A resin in which a crystal melting peak can be confirmed when measured with a DSC (differential scanning calorimeter) is defined as a crystalline resin, and a resin in which no crystal melting peak can be confirmed is defined as an amorphous resin. A thermoplastic elastomer is a material that becomes plastic at high temperatures and exhibits rubber-like elasticity at room temperature. Amorphous thermoplastic resins are not particularly limited, but examples include polystyrene resin, polymethyl methacrylate resin, vinyl chloride resin, acrylonitrile-butadiene-styrene copolymer resin, polycarbonate resin, polyacetal resin, amorphous polyester resin, and styrene-acrylic acid ester copolymer resin. The crystalline thermoplastic resin is not particularly limited, but examples include polyethylene, polypropylene, polyamide, polyacetal, crystalline polyesters such as polyethylene terephthalate, polyphenylene sulfide, and polyether ether ketone. Thermoplastic elastomers are not particularly limited, but examples include olefin-based, styrene-based, urethane-based, acrylic-based, ester-based, and polyamide-based elastomers. In order to more clearly demonstrate the effects of the surface modifier composition of the present invention, the thermoplastic resin composition of the present invention preferably contains at least one selected from the group consisting of amorphous thermoplastic resins and thermoplastic elastomers, and more preferably contains an amorphous thermoplastic resin.

[0039] Furthermore, the thermoplastic resin composition of the present invention may contain various additives that are commonly added to adjust physical properties, as necessary, within the limits that do not impair the objectives of the present invention. Examples of such additives include plasticizers, crosslinking agents, softeners, tackifiers, antistatic agents, fillers, anti-aging agents, silane coupling agents, zinc oxide, vulcanization accelerators, vulcanizing agents, work improvement agents, solvents, and the like.

[0040] The thermoplastic resin composition of the present invention can be produced by kneading the above-mentioned surface modifier composition of the present invention, a thermoplastic resin, and additives added as needed, using a known method.

[0041] The applications of the thermoplastic resin composition of the present invention are not particularly limited, but examples include electronic components, automobile parts, packaging materials, medical devices, building materials, furniture, home appliances, household goods, food containers, beverage containers, toner, and the like. [Examples]

[0042] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, parts and percentages are based on mass.

[0043] [Preparation of surface modifier composition] (1) Preparation of secondary alcohol A Five types of secondary alcohol A were prepared using the following method.

[0044] (Synthesis Example 1) Synthesis of secondary alcohol A1 (18-pentatriacontanol) 700.0 g of magnesium stearate was weighed into a 1 L stainless steel separable flask, and the system was heated to 250°C under nitrogen injection. Then, nitrogen was injected under pressure of 2 MPa, and the system temperature was raised to 340-350°C, and the reaction was continued for 8 hours. Subsequently, the reaction product was cooled to 100°C to obtain the crude ketone product. Under nitrogen injection at 100°C, the obtained crude ketone product was filtered using a 100-mesh metal strainer to remove the magnesium oxide produced as a by-product. The filtered ketone (diheptadecyl ketone) was discharged into a stainless steel tray, solidified at room temperature, and pulverized in a mixer to obtain 540 g of diheptadecyl ketone. The obtained diheptadecyl ketone was reduced by reacting it with 10 g of sodium borohydride in toluene solvent to obtain 488 g of secondary alcohol A1 (18-pentatriacontanol).

[0045] (Synthesis Example 2) Synthesis of Secondary Alcohol A2 (28-Pentapentacontanol) Secondary alcohol A2 (28-pentapentacontanol) was obtained by the same procedure as in Synthesis Example 1, except that magnesium montanate was used instead of magnesium stearate as the main raw material.

[0046] (Synthesis Example 3) Synthesis of Secondary Alcohol A3 (12-Tricosanol) Secondary alcohol A3 (12-tricosanol) was obtained by the same procedure as in Synthesis Example 1, except that magnesium laurate was used instead of magnesium stearate as the main raw material.

[0047] (Synthesis Example 4) Synthesis of secondary alcohol A4 (8-pentadecanol) Secondary alcohol A4 (8-pentadecanol) was obtained by the same procedure as in Synthesis Example 1, except that magnesium caprylate was used instead of magnesium stearate as the main raw material.

[0048] (Synthesis Example 5) Synthesis of Secondary Alcohol A5 (3,4-Heptahexacontanol) Secondary alcohol A5 (3,4-heptahexacontanol) was obtained by the same procedure as in Synthesis Example 1, except that magnesium tetratriacontanate was used instead of magnesium stearate as the main raw material.

[0049] (2) Preparation of dialkylketone B Five types of dialkylketone B were prepared using the following method.

[0050] (Synthesis Example 6) Synthesis of Dialkylketone B1 (Diheptadecylketone) Dialkylketone B1 (diheptadecylketone) was obtained using the same procedure as in Synthesis Example 1 to obtain the ketone (diheptadecylketone).

[0051] (Synthesis Example 7) Synthesis of Dialkylketone B2 (Diheptacosylketone) Except for using magnesium montanate instead of magnesium stearate as the main raw material, dialkylketone B2 (diheptacosylketone) was obtained by the same procedure as in Synthesis Example 1 for obtaining the ketone (diheptadecylketone).

[0052] (Synthesis Example 8) Synthesis of dialkylketone B3 (diundecylketone) Except for using magnesium laurate instead of magnesium stearate as the main raw material, dialkylketone B3 (diundecylketone) was obtained by the same procedure as in Synthesis Example 1 to obtain the ketone (diheptadecylketone).

[0053] (Synthesis Example 9) Synthesis of Dialkylketone B4 (Diheptyl Ketone) Except for using magnesium caprylate instead of magnesium stearate as the main raw material, dialkylketone B4 (diheptyl ketone) was obtained by the same procedure as in Synthesis Example 1 for obtaining the ketone (diheptadecyl ketone).

[0054] (Synthesis Example 10) Synthesis of Dialkylketone B5 (Ditritriacontanyl Ketone) Except for using magnesium tetratriacontanate instead of magnesium stearate as the main raw material, dialkylketone B5 (ditritricontanyl ketone) was obtained by the same procedure as in Synthesis Example 1 to obtain the ketone (diheptadecyl ketone).

[0055] Table 1 shows the compound names and carbon numbers of secondary alcohols A1 to A5 obtained in Synthesis Examples 1 to 5, and Table 2 shows the compound names and carbon numbers of dialkylketones B1 to B5 obtained in Synthesis Examples 6 to 10.

[0056] [Table 1]

[0057] [Table 2]

[0058] (3) Preparation of surface modifier composition Surface modifier compositions (surface modifier compositions W1 to W12) were prepared using the following method.

[0059] [Preparation of surface modifier composition W1] 99 g of secondary alcohol A1 and 1 g of dialkylketone B1 were taken, heated and dissolved at 90°C, mixed until homogeneous, cooled and solidified, and then pulverized to obtain surface modifier composition W1.

[0060] [Preparation of surface modifier compositions W2 to W12] Surface modifier compositions W2 to W12 were obtained in the same manner as surface modifier composition 1, except that the combination or mass ratio of secondary alcohol A and dialkylketone B was changed according to Table 3.

[0061] Table 3 shows the secondary alcohol A and dialkylketone B contained in surface modifier compositions W1 to W12, the mass ratio of secondary alcohol A to dialkylketone B (A:B), and the difference (|ab|) between the number of carbon atoms a of secondary alcohol A and the number of carbon atoms b of dialkylketone B.

[0062] [Table 3]

[0063] Surface modifier compositions W1 to W8 were surface modifier compositions of the present invention, comprising a secondary alcohol A having 23 to 61 carbon atoms and a dialkylketone B having 23 to 61 carbon atoms, with the mass ratio of secondary alcohol A to dialkylketone B being in the range of 70:30 to 99.9:0.1. Furthermore, in surface modifier compositions W1 to W8, the difference (|ab|) between the number of carbon atoms a of secondary alcohol A and the number of carbon atoms b of dialkylketone B was 0 or more and 20 or less. On the other hand, surface modifier composition W9 consisted only of secondary alcohol A and did not contain dialkylketone B. The surface modifier composition W10 had a mass ratio (A:B) of 60:40 between secondary alcohol A and dialkylketone B, which was outside the range of 70:30 to 99.9:0.1. Surface modifier composition W11 contained a secondary alcohol with 15 carbon atoms and a dialkyl ketone with 15 carbon atoms instead of secondary alcohol A with 23 to 61 carbon atoms and dialkyl ketone B with 23 to 61 carbon atoms. The surface modifier composition W12 contained a secondary alcohol with 67 carbon atoms and a dialkyl ketone with 67 carbon atoms instead of secondary alcohol A with 23 to 61 carbon atoms and dialkyl ketone B with 23 to 61 carbon atoms.

[0064] [Example 1: Preparation of thermoplastic resin composition R1] 0.05 g of surface modifier composition W1 was weighed out and mixed with 0.95 g of polycarbonate (Mitsubishi Engineering Plastics Co., Ltd., "Yupilon S1000") as a thermoplastic resin. The mixture was melt-kneaded at 260°C in a twin-screw kneader, cooled, and then pulverized to prepare thermoplastic resin composition R1.

[0065] [Examples 2-9 and Comparative Examples 1-4: Preparation of Thermoplastic Resin Compositions R2-R13] Thermoplastic resin compositions R2 to R13 were prepared in the same manner as thermoplastic resin composition R1, except that the combination of thermoplastic resin and surface modifier composition was changed according to Table 4. The thermoplastic resins used are as follows: Yupilon S1000: Manufactured by Mitsubishi Engineering Plastics, made of polycarbonate. JSR 1500: Manufactured by JSR Corporation, styrene-butadiene rubber (thermoplastic elastomer)

[0066] [Evaluation of thermoplastic resin compositions] The following evaluations were performed on the obtained thermoplastic resin compositions R1 to R13.

[0067] (1) Slipperiness The thermoplastic resin composition was molded into cylindrical pellets with a diameter of 5 cm and a thickness of 5 mm using a tablet molding machine (product name: Tabletop hydraulic molding machine MP250, manufactured by Maarsen). The bottom surface of the pellets was heated for 1 second on a hot plate set to the same temperature as the mixing temperature (260°C), and then rapidly cooled to room temperature. The coefficient of dynamic friction of the heated surface of the pellets was measured using a Bowden tester with a contact probe (semi-cylindrical, stainless steel, 1 cm in diameter) under the following conditions: load: 100 g, speed: 2.5 mm / s, measurement distance: 10 mm, and number of tests: 10. The average of the 10 measured values ​​was taken as the coefficient of dynamic friction μ of the thermoplastic resin composition. The coefficient of dynamic friction was similarly determined for thermoplastic resins without the addition of a surface modifier composition, and this was defined as the coefficient of dynamic friction μBlank for the thermoplastic resin. Using the values ​​of the kinetic friction coefficient μ and the kinetic friction coefficient μBlank, Kμ was calculated using the following equation (1). Kμ = μ / μBlank Equation (1) The smaller the Kμ value, the better the lubricity-improving effect of the surface modifier composition. The lubricity-improving effect was evaluated based on the Kμ value. The evaluation criteria are as follows: ◎: Kμ<0.80 ○: 0.80 ≤ Kμ < 0.90 ×: 0.90 ≤ Kμ Table 4 shows the evaluation results of the lubricity improvement effect, with the Kμ value in parentheses.

[0068] (2) Sliding property after water resistance test Water resistance test was carried out on the pellets used in the evaluation of the above "(1) Sliding property". Specifically, the pellets were immersed in pure water at 40°C for 1 hour. Then, the pellets were taken out, and the water adhering to the pellets was completely wiped off with an acrylic fiber wiping sheet. Thereafter, the pellets were dried at room temperature for 24 hours. Repeating this series of operations (immersion in pure water, wiping of water, and drying) 10 times was defined as the water resistance test. The bottom surface of the pellets after the water resistance test was heated on a hot plate set at the same temperature as the kneading temperature (260°C) for 1 second and then rapidly cooled at room temperature. For the heated surface of the pellets, the coefficient of kinetic friction was measured under the same conditions as those for the measurement of the coefficient of kinetic friction μ in the evaluation of the above "(1) Sliding property". The average value of the 10 measured values was taken as the coefficient of kinetic friction μ' of the thermoplastic resin composition after the water resistance test. Using the value of the coefficient of kinetic friction μ' and the value of the coefficient of kinetic friction μBlank of the thermoplastic resin that has not undergone the water resistance test and to which the surface modifier composition has not been added, Kμ' was calculated by the following formula (1'). Kμ' = μ' / μBlank Formula (1') The smaller the value of Kμ', the more excellent the effect of improving the sliding property by the surface modifier composition even after the water resistance test. Based on the value of Kμ', the effect of improving the sliding property after the water resistance test was evaluated. The evaluation criteria are as follows. ◎: Kμ' < 0.80 〇: 0.80 ≤ Kμ' < 0.90 ×: 0.90 ≤ Kμ' Table 4 shows the evaluation results of the effect of improving the sliding property after the water resistance test and the value of Kμ' in parentheses.

[0069] (3) Water resistance Pellets similar to the cylindrical pellets used in the evaluation of the above "(1) Sliding property" were prepared and used as measurement samples. For 10 measurement regions on the surface of the samples, using "Gloss Checker IG - 320" manufactured by Horiba, Ltd., measurement was carried out under the condition of an incident angle of 60°C, and the average value was taken as the gloss value G of the thermoplastic resin composition. Thereafter, the same test as the water resistance test conducted in the evaluation of the above-mentioned "(2) Sliding property after the water resistance test" was carried out on the above-mentioned measurement sample to obtain a sample after the water resistance test. For the sample after the water resistance test, the gloss value was measured under the same conditions as when the above-mentioned gloss value G was obtained, and the average value was taken as the gloss value G' of the thermoplastic resin composition after the water resistance test. Using the value of the gloss value G of the thermoplastic resin composition and the value of the gloss value G' of the thermoplastic resin composition after the water resistance test, the change rate ΔG of the gloss value of the thermoplastic resin composition before and after the water resistance test was calculated by the following formula (2). ΔG = |G - G′| / G Formula (2) The smaller the value of the change rate ΔG of the gloss value, the less the gloss of the sample has changed before and after the water resistance test. Based on the value of ΔG, the water resistance was evaluated. The evaluation criteria are as follows. ◎: ΔG < 0.05 〇: 0.05 ≤ ΔG < 0.10 ×: 0.10 ≤ ΔG Table 4 shows the evaluation results of the water resistance based on the gloss change before and after the water resistance test, and the value of ΔG is shown in parentheses.

[0070] 〔Reference Examples 1 - 2〕 For reference, the same evaluation was also carried out on the thermoplastic resin alone used in the above-mentioned Examples and Comparative Examples. The evaluation results are shown in Table 4.

[0071]

Table 4

[0072] Although the sliding properties of the thermoplastic resin compositions R10 - R13 containing any of the surface modifier compositions W9 - W12 in Comparative Examples 1 - 4 were improved compared to the thermoplastic resin alone, sufficient sliding properties that could maintain good sliding properties even after the water resistance test were not imparted. Also, for the thermoplastic resin compositions R10 - R13, the change rate ΔG of the gloss value before and after the water resistance test was large, and the water resistance was not improved. In contrast, the thermoplastic resin compositions R1 to R9 of Examples 1 to 9, which contained any of the surface modifier compositions W1 to W8, exhibited improved slipperiness compared to the thermoplastic resin alone, and were given sufficient slipperiness to maintain good slipperiness even after the water resistance test. Furthermore, the thermoplastic resin compositions R1 to R9 showed a small change in gloss value ΔG before and after the water resistance test, indicating improved water resistance. Therefore, the surface modifier compositions W1 to W8 were able to impart excellent slipperiness and water resistance to the thermoplastic resin. [Industrial applicability]

[0073] The surface modifier composition of the present invention can improve the slipperiness and water resistance of the surface of thermoplastic resins. Therefore, the surface modifier composition of the present invention is particularly useful in applications where slipperiness and water resistance are required for thermoplastic resin molded products, specifically in automotive exterior parts, packaging materials, and building materials.

Claims

1. A surface modifier composition for thermoplastic resins, comprising a secondary alcohol A having 23 to 61 carbon atoms and a dialkylketone B having 23 to 61 carbon atoms, wherein the mass ratio of the secondary alcohol A to the dialkylketone B (secondary alcohol A:dialkylketone B) is 70:30 to 99.9:0.

1.

2. A thermoplastic resin composition comprising the surface modifier composition for thermoplastic resins described in claim 1 and a thermoplastic resin.

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